# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

A novel emitter compound having the formula Os(L1)(L2)(L3) and a novel method of making such compounds are disclosed. In the formula Os(L1)(L2)(L3), each of L1, L2, and L3 is independently a bidentate ligand. The method includes (a) reacting a precursor of ligand L1 with an osmium precursor to form a first intermediate product that has the ligand L1 coordinated to the osmium, wherein the osmium precursor has the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; (b) reacting the first intermediate product with a reducing agent to form a Os(II) second intermediate product; (c) reacting the second intermediate product with a coordinating solvent to form a third intermediate product; and (d) reacting a mixture of ligands L2 and L3 with said third intermediate product.

## Background
PARTIES TO A JOINT RESEARCH AGREEMENT
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.


FIELD OF THE INVENTION
The present invention relates to compounds for use as emitters and devices, such as organic light emitting diodes, including the same. More particularly, the compounds disclosed herein are novel phosphorus containing tris(bidentate) osmium complexes.
BACKGROUND
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:




In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
SUMMARY
According to an embodiment, a method of making a compound having the formula Os(L1)(L2)(L3), wherein each of L1, L2, and L3 is independently a bidentate ligand is disclosed. The method comprises: (a) reacting a precursor of ligand L1 with an osmium precursor to form a first intermediate product that has the ligand L1 coordinated to the osmium, wherein the osmium precursor has the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl; (b) reacting the first intermediate product with a reducing agent to form a Os(II) second intermediate product; (c) reacting the second intermediate product with a coordinating solvent to form a third intermediate product; and (d) reacting a mixture of ligands L2 and L3 with said third intermediate product.
According to another aspect of the present disclosure, a compound having the formula Os(L1)(L2)(L3) is disclosed, wherein L1, L2 and L3 are independently a bidentate ligand; and wherein each of L1, L2, and L3 is different from each other.
According to another aspect, a first device comprising a first organic light emitting device is provided. The first organic light emitting device can comprise an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound having the formula Os(L1)(L2)(L3), wherein L1, L2, and L3 are independently a bidentate ligand, and wherein each of L1, L2, and L3 is different from each other. The first device can be a consumer product, an organic light-emitting device, and/or a lighting panel.
The compounds disclosed herein are novel ancillary ligands for metal complexes. The incorporation of these ligands can narrow the emission spectrum, decrease evaporation temperature, and improve device efficiency. The inventors have discovered that incorporating these novel ancillary ligands in iridium complexes improved sublimation of the resulting iridium complexes, color spectrum of phosphorescence by these iridium complexes, and their EQE.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an organic light emitting device.
FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
FIG. 3 shows molecular diagram of an osmium tribidentate complex, trisbidentatecomplex-Bi2 (1), disclosed herein with X-ray diffraction analysis characterization.
FIG. 4 shows molecular diagram of another osmium tribidentate complex, trisbidentatecomplex-Bi3 (2), disclosed herein with X-ray diffraction analysis characterization.



DETAILED DESCRIPTION
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting.
For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon. Thus, where R2 is monosubstituted, then one R2 must be other than H. Similarly, where R3 is disubstituted, then two of R3 must be other than H. Similarly, where R2 is unsubstituted R2 is hydrogen for all available positions.
According to an aspect of the present disclosure, a novel osmium(II) complexes comprising three different bidentate ligands are disclosed. According to another aspect, a synthetic method for making such Os(II) complexes is provided.
Osmium (II) complexes have been investigated for OLED applications. The octahedral ligand arrangement of the Os(II) complexes resembles that of Ir(III) complexes. Os(II) complexes generally exhibit low oxidation potential, i.e. shallow HOMO energy level than Ir(III) complexes. Tris-bidentate Os(II) carbene complexes offer unique advantages for OLED applications. It offers a great deal of flexibility for color tuning and bring the HOMO level to proper alignment with the device.
Although US 2009/0001875 disclosed tris-bidentate Os(II) complexes, in those tris-bidentate Os(II) complexes, two of the bidentate ligands binding to Os(II) metal are identical. The inventors have discovered that further benefits are achieved when three different bidentate ligands are coordinated to Os(II) metal to form a heteroleptic complex. For example, the thermal properties, electrochemical properties, and photophysical properties can be tuned by selecting three proper ligands. It offers more flexibility for materials design than two identical ligands.
Such osmium complexes comprising three different bidentate ligands have never been synthesized before the invention disclosed herein. These novel complexes are useful compounds for phosphorescent emitters. One aspect of the present disclosure also provides a new method developed by the inventors for synthesizing such tris-bidentate Os(II) complexes where the Os(II) complexes comprise three different bidentate ligands. This method is, however, suitable for making both heteroleptic and homoleptic tris-bidentate Os(II) complexes.
As shown in the scheme below, (a) an osmium precursor is first reacted with a precursor of bidentate ligand L1 to form a first intermediate product that has the bidentate ligand L1 coordinated to the osmium atom, wherein the osmium precursor has the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl. Then, (b) the first intermediate product is reacted with a reducing agent to form a Os(II) second intermediate product. Then, (c) the second with a reducing agent to form a Os(II) second intermediate product. Then, (c) the second intermediate product is reacted with a coordinating solvent to form a third intermediate product. Next, (d) a mixture of precursors of bidentate ligands L2 and L3 is reacted with the third intermediate product to obtain the final complex.
In one embodiment of the method, R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, and 2-methylphenyl. In another embodiment, R is 1-methylethyl.
In one embodiment of the method, the osmium precursor has the formula OsH6(PiPr3)2.
In one embodiment of the method, the ligand L1 has at least one coordinating atom of carbene. In another embodiment, the ligand L1 is a monoanionic bidentate ligand, L2 is a monoanionic bidentate ligand, and L3 is a neutral bidentate ligand.
In one embodiment of the method, the ligands L1, L2, and L3 are independently selected from the group LIST-A consisting of:




wherein C is a monoanionic carbon coordinating atom, C′ and C′′ are each a neutral carbene coordinating atom, N is a neutral nitrogen coordinating atom, N′ is an anionic nitrogen coordinating atom, P and P′ are each a neutral phosphorus coordinating atom, O is a monoanionic oxygen coordinating atom, and O′ is a neutral oxygen coordinating atom.

According to another aspect, the ligands L1, L2, and L3 are independently selected from the group LIST-B consisting of:













wherein Ra, Rb, Rc, Rd, and Re are each independently mono, di, tri, or tetra substitutions;

wherein Ra, Rb, Rc, Rd, and Re are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein two adjacent substituents of Ra, Rb, Rc, Rd, and Re are optionally joined to form a fused ring and may be further substituted, wherein the dash lines show the connection points to osmium.
According to another aspect, the ligands L1, L2, and L3 are independently selected from the group LIST-C consisting of:

























wherein the dash lines show the connection points to osmium.

According to another aspect, the ligands L1, L2, and L3 are independently selected from the group LIST-D consisting of:

























wherein the dash lines show the connection points to osmium.

According to another aspect, the compound having the formula Os(L1)(L2)(L3) is selected from the group consisting of Compounds 1 to 4176 defined in Table 1 below:












TABLE 1







Compound






number
L1
L2
L3





















1.
L101
L102
L102



2.
L101
L103
L144



3.
L101
L104
L144



4.
L101
L105
L144



5.
L101
L106
L144



6.
L101
L107
L144



7.
L101
L108
L144



8.
L101
L109
L144



9.
L101
L110
L144



10.
L101
L111
L144



11.
L101
L112
L144



12.
L101
L113
L144



13.
L101
L114
L144



14.
L101
L115
L144



15.
L101
L116
L144



16.
L101
L117
L144



17.
L101
L118
L144



18.
L101
L119
L144



19.
L101
L130
L144



20.
L101
L131
L144



21.
L101
L132
L144



22.
L101
L133
L144



23.
L101
L134
L144



24.
L101
L140
L144



25.
L101
L141
L144



26.
L101
L159
L144



27.
L101
L160
L144



28.
L101
L102
L145



29.
L101
L103
L145



30.
L101
L104
L145



31.
L101
L105
L145



32.
L101
L106
L145



33.
L101
L107
L145



34.
L101
L108
L145



35.
L101
L109
L145



36.
L101
L110
L145



37.
L101
L111
L145



38.
L101
L112
L145



39.
L101
L113
L145



40.
L101
L114
L145



41.
L101
L115
L145



42.
L101
L116
L145



43.
L101
L117
L145



44.
L101
L118
L145



45.
L101
L119
L145



46.
L101
L130
L145



47.
L101
L131
L145



48.
L101
L132
L145



49.
L101
L133
L145



50.
L101
L134
L145



51.
L101
L140
L145



52.
L101
L141
L145



53.
L101
L159
L145



54.
L101
L160
L145



55.
L101
L102
L147



56.
L101
L103
L147



57.
L101
L104
L147



58.
L101
L105
L147



59.
L101
L106
L147



60.
L101
L107
L147



61.
L101
L108
L147



62.
L101
L109
L147



63.
L101
L110
L147



64.
L101
L111
L147



65.
L101
L112
L147



66.
L101
L113
L147



67.
L101
L114
L147



68.
L101
L115
L147



69.
L101
L116
L147



70.
L101
L117
L147



71.
L101
L118
L147



72.
L101
L119
L147



73.
L101
L130
L147



74.
L101
L131
L147



75.
L101
L132
L147



76.
L101
L133
L147



77.
L101
L134
L147



78.
L101
L140
L147



79.
L101
L141
L147



80.
L101
L159
L147



81.
L101
L160
L147



82.
L101
L102
L149



83.
L101
L103
L149



84.
L101
L104
L149



85.
L101
L105
L149



86.
L101
L106
L149



87.
L101
L107
L149



88.
L101
L108
L149



89.
L101
L109
L149



90.
L101
L110
L149



91.
L101
L111
L149



92.
L101
L112
L149



93.
L101
L113
L149



94.
L101
L114
L149



95.
L101
L115
L149



96.
L101
L116
L149



97.
L101
L117
L149



98.
L101
L118
L149



99.
L101
L119
L149



100.
L101
L130
L149



101.
L101
L131
L149



102.
L101
L132
L149



103.
L101
L133
L149



104.
L101
L134
L149



105.
L101
L140
L149



106.
L101
L141
L149



107.
L101
L159
L149



108.
L101
L160
L149



109.
L101
L102
L152



110.
L101
L103
L152



111.
L101
L104
L152



112.
L101
L105
L152



113.
L101
L106
L152



114.
L101
L107
L152



115.
L101
L108
L152



116.
L101
L109
L152



117.
L101
L110
L152



118.
L101
L111
L152



119.
L101
L112
L152



120.
L101
L113
L152



121.
L101
L114
L152



122.
L101
L115
L152



123.
L101
L116
L152



124.
L101
L117
L152



125.
L101
L118
L152



126.
L101
L119
L152



127.
L101
L130
L152



128.
L101
L131
L152



129.
L101
L132
L152



130.
L101
L133
L152



131.
L101
L134
L152



132.
L101
L140
L152



133.
L101
L141
L152



134.
L101
L159
L152



135.
L101
L160
L152



136.
L101
L102
L164



137.
L101
L103
L164



138.
L101
L104
L164



139.
L101
L105
L164



140.
L101
L106
L164



141.
L101
L107
L164



142.
L101
L108
L164



143.
L101
L109
L164



144.
L101
L110
L164



145.
L101
L111
L164



146.
L101
L112
L164



147.
L101
L113
L164



148.
L101
L114
L164



149.
L101
L115
L164



150.
L101
L116
L164



151.
L101
L117
L164



152.
L101
L118
L164



153.
L101
L119
L164



154.
L101
L130
L164



155.
L101
L131
L164



156.
L101
L132
L164



157.
L101
L133
L164



158.
L101
L134
L164



159.
L101
L140
L164



160.
L101
L141
L164



161.
L101
L159
L164



162.
L101
L160
L164



163.
L101
L102
L165



164.
L101
L103
L165



165.
L101
L104
L165



166.
L101
L105
L165



167.
L101
L106
L165



168.
L101
L107
L165



169.
L101
L108
L165



170.
L101
L109
L165



171.
L101
L110
L165



172.
L101
L111
L165



173.
L101
L112
L165



174.
L101
L113
L165



175.
L101
L114
L165



176.
L101
L115
L165



177.
L101
L116
L165



178.
L101
L117
L165



179.
L101
L118
L165



180.
L101
L119
L165



181.
L101
L130
L165



182.
L101
L131
L165



183.
L101
L132
L165



184.
L101
L133
L165



185.
L101
L134
L165



186.
L101
L140
L165



187.
L101
L141
L165



188.
L101
L159
L165



189.
L101
L160
L165



190.
L101
L102
L166



191.
L101
L103
L166



192.
L101
L104
L166



193.
L101
L105
L166



194.
L101
L106
L166



195.
L101
L107
L166



196.
L101
L108
L166



197.
L101
L109
L166



198.
L101
L110
L166



199.
L101
L111
L166



200.
L101
L112
L166



201.
L101
L113
L166



202.
L101
L114
L166



203.
L101
L115
L166



204.
L101
L116
L166



205.
L101
L117
L166



206.
L101
L118
L166



207.
L101
L119
L166



208.
L101
L130
L166



209.
L101
L131
L166



210.
L101
L132
L166



211.
L101
L133
L166



212.
L101
L134
L166



213.
L101
L140
L166



214.
L101
L141
L166



215.
L101
L159
L166



216.
L101
L160
L166



217.
L101
L102
L170



218.
L101
L103
L170



219.
L101
L104
L170



220.
L101
L105
L170



221.
L101
L106
L170



222.
L101
L107
L170



223.
L101
L108
L170



224.
L101
L109
L170



225.
L101
L110
L170



226.
L101
L111
L170



227.
L101
L112
L170



228.
L101
L113
L170



229.
L101
L114
L170



230.
L101
L115
L170



231.
L101
L116
L170



232.
L101
L117
L170



233.
L101
L118
L170



234.
L101
L119
L170



235.
L101
L130
L170



236.
L101
L131
L170



237.
L101
L132
L170



238.
L101
L133
L170



239.
L101
L134
L170



240.
L101
L140
L170



241.
L101
L141
L170



242.
L101
L159
L170



243.
L101
L160
L170



244.
L101
L102
L174



245.
L101
L103
L174



246.
L101
L104
L174



247.
L101
L105
L174



248.
L101
L106
L174



249.
L101
L107
L174



250.
L101
L108
L174



251.
L101
L109
L174



252.
L101
L110
L174



253.
L101
L111
L174



254.
L101
L112
L174



255.
L101
L113
L174



256.
L101
L114
L174



257.
L101
L115
L174



258.
L101
L116
L174



259.
L101
L117
L174



260.
L101
L118
L174



261.
L101
L119
L174



262.
L101
L130
L174



263.
L101
L131
L174



264.
L101
L132
L174



265.
L101
L133
L174



266.
L101
L134
L174



267.
L101
L140
L174



268.
L101
L141
L174



269.
L101
L159
L174



270.
L101
L160
L174



271.
L101
L102
L176



272.
L101
L103
L176



273.
L101
L104
L176



274.
L101
L105
L176



275.
L101
L106
L176



276.
L101
L107
L176



277.
L101
L108
L176



278.
L101
L109
L176



279.
L101
L110
L176



280.
L101
L111
L176



281.
L101
L112
L176



282.
L101
L113
L176



283.
L101
L114
L176



284.
L101
L115
L176



285.
L101
L116
L176



286.
L101
L117
L176



287.
L101
L118
L176



288.
L101
L119
L176



289.
L101
L130
L176



290.
L101
L131
L176



291.
L101
L132
L176



292.
L101
L133
L176



293.
L101
L134
L176



294.
L101
L140
L176



295.
L101
L141
L176



296.
L101
L159
L176



297.
L101
L160
L176



298.
L101
L102
L179



299.
L101
L103
L179



300.
L101
L104
L179



301.
L101
L105
L179



302.
L101
L106
L179



303.
L101
L107
L179



304.
L101
L108
L179



305.
L101
L109
L179



306.
L101
L110
L179



307.
L101
L111
L179



308.
L101
L112
L179



309.
L101
L113
L179



310.
L101
L114
L179



311.
L101
L115
L179



312.
L101
L116
L179



313.
L101
L117
L179



314.
L101
L118
L179



315.
L101
L119
L179



316.
L101
L130
L179



317.
L101
L131
L179



318.
L101
L132
L179



319.
L101
L133
L179



320.
L101
L134
L179



321.
L101
L140
L179



322.
L101
L141
L179



323.
L101
L159
L179



324.
L101
L160
L179



325.
L101
L102
L180



326.
L101
L103
L180



327.
L101
L104
L180



328.
L101
L105
L180



329.
L101
L106
L180



330.
L101
L107
L180



331.
L101
L108
L180



332.
L101
L109
L180



333.
L101
L110
L180



334.
L101
L111
L180



335.
L101
L112
L180



336.
L101
L113
L180



337.
L101
L114
L180



338.
L101
L115
L180



339.
L101
L116
L180



340.
L101
L117
L180



341.
L101
L118
L180



342.
L101
L119
L180



343.
L101
L130
L180



344.
L101
L131
L180



345.
L101
L132
L180



346.
L101
L133
L180



347.
L101
L134
L180



348.
L101
L140
L180



349.
L101
L141
L180



350.
L101
L159
L180



351.
L101
L160
L180



352.
L102
L103
L144



353.
L102
L104
L144



354.
L102
L105
L144



355.
L102
L106
L144



356.
L102
L107
L144



357.
L102
L108
L144



358.
L102
L109
L144



359.
L102
L110
L144



360.
L102
L111
L144



361.
L102
L112
L144



362.
L102
L113
L144



363.
L102
L114
L144



364.
L102
L115
L144



365.
L102
L116
L144



366.
L102
L117
L144



367.
L102
L118
L144



368.
L102
L119
L144



369.
L102
L130
L144



370.
L102
L131
L144



371.
L102
L132
L144



372.
L102
L133
L144



373.
L102
L134
L144



374.
L102
L140
L144



375.
L102
L141
L144



376.
L102
L159
L144



377.
L102
L160
L144



378.
L102
L103
L145



379.
L102
L104
L145



380.
L102
L105
L145



381.
L102
L106
L145



382.
L102
L107
L145



383.
L102
L108
L145



384.
L102
L109
L145



385.
L102
L110
L145



386.
L102
L111
L145



387.
L102
L112
L145



388.
L102
L113
L145



389.
L102
L114
L145



390.
L102
L115
L145



391.
L102
L116
L145



392.
L102
L117
L145



393.
L102
L118
L145



394.
L102
L119
L145



395.
L102
L130
L145



396.
L102
L131
L145



397.
L102
L132
L145



398.
L102
L133
L145



399.
L102
L134
L145



400.
L102
L140
L145



401.
L102
L141
L145



402.
L102
L159
L145



403.
L102
L160
L145



404.
L102
L103
L147



405.
L102
L104
L147



406.
L102
L105
L147



407.
L102
L106
L147



408.
L102
L107
L147



409.
L102
L108
L147



410.
L102
L109
L147



411.
L102
L110
L147



412.
L102
L111
L147



413.
L102
L112
L147



414.
L102
L113
L147



415.
L102
L114
L147



416.
L102
L115
L147



417.
L102
L116
L147



418.
L102
L117
L147



419.
L102
L118
L147



420.
L102
L119
L147



421.
L102
L130
L147



422.
L102
L131
L147



423.
L102
L132
L147



424.
L102
L133
L147



425.
L102
L134
L147



426.
L102
L140
L147



427.
L102
L141
L147



428.
L102
L159
L147



429.
L102
L160
L147



430.
L102
L103
L149



431.
L102
L104
L149



432.
L102
L105
L149



433.
L102
L106
L149



434.
L102
L107
L149



435.
L102
L108
L149



436.
L102
L109
L149



437.
L102
L110
L149



438.
L102
L111
L149



439.
L102
L112
L149



440.
L102
L113
L149



441.
L102
L114
L149



442.
L102
L115
L149



443.
L102
L116
L149



444.
L102
L117
L149



445.
L102
L118
L149



446.
L102
L119
L149



447.
L102
L130
L149



448.
L102
L131
L149



449.
L102
L132
L149



450.
L102
L133
L149



451.
L102
L134
L149



452.
L102
L140
L149



453.
L102
L141
L149



454.
L102
L159
L149



455.
L102
L160
L149



456.
L102
L103
L152



457.
L102
L104
L152



458.
L102
L105
L152



459.
L102
L106
L152



460.
L102
L107
L152



461.
L102
L108
L152



462.
L102
L109
L152



463.
L102
L110
L152



464.
L102
L111
L152



465.
L102
L112
L152



466.
L102
L113
L152



467.
L102
L114
L152



468.
L102
L115
L152



469.
L102
L116
L152



470.
L102
L117
L152



471.
L102
L118
L152



472.
L102
L119
L152



473.
L102
L130
L152



474.
L102
L131
L152



475.
L102
L132
L152



476.
L102
L133
L152



477.
L102
L134
L152



478.
L102
L140
L152



479.
L102
L141
L152



480.
L102
L159
L152



481.
L102
L160
L152



482.
L102
L103
L164



483.
L102
L104
L164



484.
L102
L105
L164



485.
L102
L106
L164



486.
L102
L107
L164



487.
L102
L108
L164



488.
L102
L109
L164



489.
L102
L110
L164



490.
L102
L111
L164



491.
L102
L112
L164



492.
L102
L113
L164



493.
L102
L114
L164



494.
L102
L115
L164



495.
L102
L116
L164



496.
L102
L117
L164



497.
L102
L118
L164



498.
L102
L119
L164



499.
L102
L130
L164



500.
L102
L131
L164



501.
L102
L132
L164



502.
L102
L133
L164



503.
L102
L134
L164



504.
L102
L140
L164



505.
L102
L141
L164



506.
L102
L159
L164



507.
L102
L160
L164



508.
L102
L103
L165



509.
L102
L104
L165



510.
L102
L105
L165



511.
L102
L106
L165



512.
L102
L107
L165



513.
L102
L108
L165



514.
L102
L109
L165



515.
L102
L110
L165



516.
L102
L111
L165



517.
L102
L112
L165



518.
L102
L113
L165



519.
L102
L114
L165



520.
L102
L115
L165



521.
L102
L116
L165



522.
L102
L117
L165



523.
L102
L118
L165



524.
L102
L119
L165



525.
L102
L130
L165



526.
L102
L131
L165



527.
L102
L132
L165



528.
L102
L133
L165



529.
L102
L134
L165



530.
L102
L140
L165



531.
L102
L141
L165



532.
L102
L159
L165



533.
L102
L160
L165



534.
L102
L103
L166



535.
L102
L104
L166



536.
L102
L105
L166



537.
L102
L106
L166



538.
L102
L107
L166



539.
L102
L108
L166



540.
L102
L109
L166



541.
L102
L110
L166



542.
L102
L111
L166



543.
L102
L112
L166



544.
L102
L113
L166



545.
L102
L114
L166



546.
L102
L115
L166



547.
L102
L116
L166



548.
L102
L117
L166



549.
L102
L118
L166



550.
L102
L119
L166



551.
L102
L130
L166



552.
L102
L131
L166



553.
L102
L132
L166



554.
L102
L133
L166



555.
L102
L134
L166



556.
L102
L140
L166



557.
L102
L141
L166



558.
L102
L159
L166



559.
L102
L160
L166



560.
L102
L103
L170



561.
L102
L104
L170



562.
L102
L105
L170



563.
L102
L106
L170



564.
L102
L107
L170



565.
L102
L108
L170



566.
L102
L109
L170



567.
L102
L110
L170



568.
L102
L111
L170



569.
L102
L112
L170



570.
L102
L113
L170



571.
L102
L114
L170



572.
L102
L115
L170



573.
L102
L116
L170



574.
L102
L117
L170



575.
L102
L118
L170



576.
L102
L119
L170



577.
L102
L130
L170



578.
L102
L131
L170



579.
L102
L132
L170



580.
L102
L133
L170



581.
L102
L134
L170



582.
L102
L140
L170



583.
L102
L141
L170



584.
L102
L159
L170



585.
L102
L160
L170



586.
L102
L103
L174



587.
L102
L104
L174



588.
L102
L105
L174



589.
L102
L106
L174



590.
L102
L107
L174



591.
L102
L108
L174



592.
L102
L109
L174



593.
L102
L110
L174



594.
L102
L111
L174



595.
L102
L112
L174



596.
L102
L113
L174



597.
L102
L114
L174



598.
L102
L115
L174



599.
L102
L116
L174



600.
L102
L117
L174



601.
L102
L118
L174



602.
L102
L119
L174



603.
L102
L130
L174



604.
L102
L131
L174



605.
L102
L132
L174



606.
L102
L133
L174



607.
L102
L134
L174



608.
L102
L140
L174



609.
L102
L141
L174



610.
L102
L159
L174



611.
L102
L160
L174



612.
L102
L103
L176



613.
L102
L104
L176



614.
L102
L105
L176



615.
L102
L106
L176



616.
L102
L107
L176



617.
L102
L108
L176



618.
L102
L109
L176



619.
L102
L110
L176



620.
L102
L111
L176



621.
L102
L112
L176



622.
L102
L113
L176



623.
L102
L114
L176



624.
L102
L115
L176



625.
L102
L116
L176



626.
L102
L117
L176



627.
L102
L118
L176



628.
L102
L119
L176



629.
L102
L130
L176



630.
L102
L131
L176



631.
L102
L132
L176



632.
L102
L133
L176



633.
L102
L134
L176



634.
L102
L140
L176



635.
L102
L141
L176



636.
L102
L159
L176



637.
L102
L160
L176



638.
L102
L103
L179



639.
L102
L104
L179



640.
L102
L105
L179



641.
L102
L106
L179



642.
L102
L107
L179



643.
L102
L108
L179



644.
L102
L109
L179



645.
L102
L110
L179



646.
L102
L111
L179



647.
L102
L112
L179



648.
L102
L113
L179



649.
L102
L114
L179



650.
L102
L115
L179



651.
L102
L116
L179



652.
L102
L117
L179



653.
L102
L118
L179



654.
L102
L119
L179



655.
L102
L130
L179



656.
L102
L131
L179



657.
L102
L132
L179



658.
L102
L133
L179



659.
L102
L134
L179



660.
L102
L140
L179



661.
L102
L141
L179



662.
L102
L159
L179



663.
L102
L160
L179



664.
L102
L103
L180



665.
L102
L104
L180



666.
L102
L105
L180



667.
L102
L106
L180



668.
L102
L107
L180



669.
L102
L108
L180



670.
L102
L109
L180



671.
L102
L110
L180



672.
L102
L111
L180



673.
L102
L112
L180



674.
L102
L113
L180



675.
L102
L114
L180



676.
L102
L115
L180



677.
L102
L116
L180



678.
L102
L117
L180



679.
L102
L118
L180



680.
L102
L119
L180



681.
L102
L130
L180



682.
L102
L131
L180



683.
L102
L132
L180



684.
L102
L133
L180



685.
L102
L134
L180



686.
L102
L140
L180



687.
L102
L141
L180



688.
L102
L159
L180



689.
L102
L160
L180



690.
L103
L104
L144



691.
L103
L105
L144



692.
L103
L106
L144



693.
L103
L107
L144



694.
L103
L108
L144



695.
L103
L109
L144



696.
L103
L110
L144



697.
L103
L111
L144



698.
L103
L112
L144



699.
L103
L113
L144



700.
L103
L114
L144



701.
L103
L115
L144



702.
L103
L116
L144



703.
L103
L117
L144



704.
L103
L118
L144



705.
L103
L119
L144



706.
L103
L130
L144



707.
L103
L131
L144



708.
L103
L132
L144



709.
L103
L133
L144



710.
L103
L134
L144



711.
L103
L140
L144



712.
L103
L141
L144



713.
L103
L159
L144



714.
L103
L160
L144



715.
L103
L104
L145



716.
L103
L105
L145



717.
L103
L106
L145



718.
L103
L107
L145



719.
L103
L108
L145



720.
L103
L109
L145



721.
L103
L110
L145



722.
L103
L111
L145



723.
L103
L112
L145



724.
L103
L113
L145



725.
L103
L114
L145



726.
L103
L115
L145



727.
L103
L116
L145



728.
L103
L117
L145



729.
L103
L118
L145



730.
L103
L119
L145



731.
L103
L130
L145



732.
L103
L131
L145



733.
L103
L132
L145



734.
L103
L133
L145



735.
L103
L134
L145



736.
L103
L140
L145



737.
L103
L141
L145



738.
L103
L159
L145



739.
L103
L160
L145



740.
L103
L104
L147



741.
L103
L105
L147



742.
L103
L106
L147



743.
L103
L107
L147



744.
L103
L108
L147



745.
L103
L109
L147



746.
L103
L110
L147



747.
L103
L111
L147



748.
L103
L112
L147



749.
L103
L113
L147



750.
L103
L114
L147



751.
L103
L115
L147



752.
L103
L116
L147



753.
L103
L117
L147



754.
L103
L118
L147



755.
L103
L119
L147



756.
L103
L130
L147



757.
L103
L131
L147



758.
L103
L132
L147



759.
L103
L133
L147



760.
L103
L134
L147



761.
L103
L140
L147



762.
L103
L141
L147



763.
L103
L159
L147



764.
L103
L160
L147



765.
L103
L104
L149



766.
L103
L105
L149



767.
L103
L106
L149



768.
L103
L107
L149



769.
L103
L108
L149



770.
L103
L109
L149



771.
L103
L110
L149



772.
L103
L111
L149



773.
L103
L112
L149



774.
L103
L113
L149



775.
L103
L114
L149



776.
L103
L115
L149



777.
L103
L116
L149



778.
L103
L117
L149



779.
L103
L118
L149



780.
L103
L119
L149



781.
L103
L130
L149



782.
L103
L131
L149



783.
L103
L132
L149



784.
L103
L133
L149



785.
L103
L134
L149



786.
L103
L140
L149



787.
L103
L141
L149



788.
L103
L159
L149



789.
L103
L160
L149



790.
L103
L104
L152



791.
L103
L105
L152



792.
L103
L106
L152



793.
L103
L107
L152



794.
L103
L108
L152



795.
L103
L109
L152



796.
L103
L110
L152



797.
L103
L111
L152



798.
L103
L112
L152



799.
L103
L113
L152



800.
L103
L114
L152



801.
L103
L115
L152



802.
L103
L116
L152



803.
L103
L117
L152



804.
L103
L118
L152



805.
L103
L119
L152



806.
L103
L130
L152



807.
L103
L131
L152



808.
L103
L132
L152



809.
L103
L133
L152



810.
L103
L134
L152



811.
L103
L140
L152



812.
L103
L141
L152



813.
L103
L159
L152



814.
L103
L160
L152



815.
L103
L104
L164



816.
L103
L105
L164



817.
L103
L106
L164



818.
L103
L107
L164



819.
L103
L108
L164



820.
L103
L109
L164



821.
L103
L110
L164



822.
L103
L111
L164



823.
L103
L112
L164



824.
L103
L113
L164



825.
L103
L114
L164



826.
L103
L115
L164



827.
L103
L116
L164



828.
L103
L117
L164



829.
L103
L118
L164



830.
L103
L119
L164



831.
L103
L130
L164



832.
L103
L131
L164



833.
L103
L132
L164



834.
L103
L133
L164



835.
L103
L134
L164



836.
L103
L140
L164



837.
L103
L141
L164



838.
L103
L159
L164



839.
L103
L160
L164



840.
L103
L104
L165



841.
L103
L105
L165



842.
L103
L106
L165



843.
L103
L107
L165



844.
L103
L108
L165



845.
L103
L109
L165



846.
L103
L110
L165



847.
L103
L111
L165



848.
L103
L112
L165



849.
L103
L113
L165



850.
L103
L114
L165



851.
L103
L115
L165



852.
L103
L116
L165



853.
L103
L117
L165



854.
L103
L118
L165



855.
L103
L119
L165



856.
L103
L130
L165



857.
L103
L131
L165



858.
L103
L132
L165



859.
L103
L133
L165



860.
L103
L134
L165



861.
L103
L140
L165



862.
L103
L141
L165



863.
L103
L159
L165



864.
L103
L160
L165



865.
L103
L104
L166



866.
L103
L105
L166



867.
L103
L106
L166



868.
L103
L107
L166



869.
L103
L108
L166



870.
L103
L109
L166



871.
L103
L110
L166



872.
L103
L111
L166



873.
L103
L112
L166



874.
L103
L113
L166



875.
L103
L114
L166



876.
L103
L115
L166



877.
L103
L116
L166



878.
L103
L117
L166



879.
L103
L118
L166



880.
L103
L119
L166



881.
L103
L130
L166



882.
L103
L131
L166



883.
L103
L132
L166



884.
L103
L133
L166



885.
L103
L134
L166



886.
L103
L140
L166



887.
L103
L141
L166



888.
L103
L159
L166



889.
L103
L160
L166



890.
L103
L104
L170



891.
L103
L105
L170



892.
L103
L106
L170



893.
L103
L107
L170



894.
L103
L108
L170



895.
L103
L109
L170



896.
L103
L110
L170



897.
L103
L111
L170



898.
L103
L112
L170



899.
L103
L113
L170



900.
L103
L114
L170



901.
L103
L115
L170



902.
L103
L116
L170



903.
L103
L117
L170



904.
L103
L118
L170



905.
L103
L119
L170



906.
L103
L130
L170



907.
L103
L131
L170



908.
L103
L132
L170



909.
L103
L133
L170



910.
L103
L134
L170



911.
L103
L140
L170



912.
L103
L141
L170



913.
L103
L159
L170



914.
L103
L160
L170



915.
L103
L104
L174



916.
L103
L105
L174



917.
L103
L106
L174



918.
L103
L107
L174



919.
L103
L108
L174



920.
L103
L109
L174



921.
L103
L110
L174



922.
L103
L111
L174



923.
L103
L112
L174



924.
L103
L113
L174



925.
L103
L114
L174



926.
L103
L115
L174



927.
L103
L116
L174



928.
L103
L117
L174



929.
L103
L118
L174



930.
L103
L119
L174



931.
L103
L130
L174



932.
L103
L131
L174



933.
L103
L132
L174



934.
L103
L133
L174



935.
L103
L134
L174



936.
L103
L140
L174



937.
L103
L141
L174



938.
L103
L159
L174



939.
L103
L160
L174



940.
L103
L104
L176



941.
L103
L105
L176



942.
L103
L106
L176



943.
L103
L107
L176



944.
L103
L108
L176



945.
L103
L109
L176



946.
L103
L110
L176



947.
L103
L111
L176



948.
L103
L112
L176



949.
L103
L113
L176



950.
L103
L114
L176



951.
L103
L115
L176



952.
L103
L116
L176



953.
L103
L117
L176



954.
L103
L118
L176



955.
L103
L119
L176



956.
L103
L130
L176



957.
L103
L131
L176



958.
L103
L132
L176



959.
L103
L133
L176



960.
L103
L134
L176



961.
L103
L140
L176



962.
L103
L141
L176



963.
L103
L159
L176



964.
L103
L160
L176



965.
L103
L104
L176



966.
L103
L105
L179



967.
L103
L106
L179



968.
L103
L107
L179



969.
L103
L108
L179



970.
L103
L109
L179



971.
L103
L110
L179



972.
L103
L111
L179



973.
L103
L112
L179



974.
L103
L113
L179



975.
L103
L114
L179



976.
L103
L115
L179



977.
L103
L116
L179



978.
L103
L117
L179



979.
L103
L118
L179



980.
L103
L119
L179



981.
L103
L130
L179



982.
L103
L131
L179



983.
L103
L132
L179



984.
L103
L133
L179



985.
L103
L134
L179



986.
L103
L140
L179



987.
L103
L141
L179



988.
L103
L159
L179



989.
L103
L160
L179



990.
L103
L104
L180



991.
L103
L105
L180



992.
L103
L106
L180



993.
L103
L107
L180



994.
L103
L108
L180



995.
L103
L109
L180



996.
L103
L110
L180



997.
L103
L111
L180



998.
L103
L112
L180



999.
L103
L113
L180



1000.
L103
L114
L180



1001
L103
L115
L180



1002.
L103
L116
L180



1003.
L103
L117
L180



1004.
L103
L118
L180



1005.
L103
L119
L180



1006.
L103
L130
L180



1007.
L103
L131
L180



1008.
L103
L132
L180



1009.
L103
L133
L180



1010
L103
L134
L180



1011
L103
L140
L180



1012.
L103
L141
L180



1013.
L103
L159
L180



1014.
L103
L160
L180



1015.
L104
L105
L144



1016.
L104
L106
L144



1017.
L104
L107
L144



1018.
L104
L108
L144



1019.
L104
L109
L144



1020.
L104
L110
L144



1021.
L104
L111
L144



1022.
L104
L112
L144



1023.
L104
L113
L144



1024.
L104
L114
L144



1025.
L104
L115
L144



1026.
L104
L116
L144



1027.
L104
L117
L144



1028.
L104
L118
L144



1029.
L104
L119
L144



1030.
L104
L130
L144



1031.
L104
L131
L144



1032.
L104
L132
L144



1033.
L104
L133
L144



1034.
L104
L134
L144



1035.
L104
L140
L144



1036.
L104
L141
L144



1037.
L104
L159
L144



1038.
L104
L160
L144



1039.
L104
L105
L145



1040.
L104
L106
L145



1041.
L104
L107
L145



1042.
L104
L108
L145



1043.
L104
L109
L145



1044.
L104
L110
L145



1045.
L104
L111
L145



1046.
L104
L112
L145



1047.
L104
L113
L145



1048.
L104
L114
L145



1049.
L104
L115
L145



1050.
L104
L116
L145



1051.
L104
L117
L145



1052.
L104
L118
L145



1053.
L104
L119
L145



1054.
L104
L130
L145



1055.
L104
L131
L145



1056.
L104
L132
L145



1057.
L104
L133
L145



1058.
L104
L134
L145



1059.
L104
L140
L145



1060.
L104
L141
L145



1061.
L104
L159
L145



1062.
L104
L160
L145



1063.
L104
L105
L147



1064.
L104
L106
L147



1065.
L104
L107
L147



1066.
L104
L108
L147



1067.
L104
L109
L147



1068.
L104
L110
L147



1069.
L104
L111
L147



1070.
L104
L112
L147



1071.
L104
L113
L147



1072.
L104
L114
L147



1073.
L104
L115
L147



1074.
L104
L116
L147



1075.
L104
L117
L147



1076.
L104
L118
L147



1077.
L104
L119
L147



1078.
L104
L130
L147



1079.
L104
L131
L147



1080.
L104
L132
L147



1081.
L104
L133
L147



1082.
L104
L134
L147



1083.
L104
L140
L147



1084.
L104
L141
L147



1085.
L104
L159
L147



1086.
L104
L160
L147



1087.
L104
L105
L149



1088.
L104
L106
L149



1089.
L104
L107
L149



1090.
L104
L108
L149



1091.
L104
L109
L149



1092.
L104
L110
L149



1093.
L104
L111
L149



1094.
L104
L112
L149



1095.
L104
L113
L149



1096.
L104
L114
L149



1097.
L104
L115
L149



1098.
L104
L116
L149



1099.
L104
L117
L149



1100.
L104
L118
L149



1101.
L104
L119
L149



1102.
L104
L130
L149



1103.
L104
L131
L149



1104.
L104
L132
L149



1105.
L104
L133
L149



1106.
L104
L134
L149



1107.
L104
L140
L149



1108.
L104
L141
L149



1109.
L104
L159
L149



1110.
L104
L160
L149



1111.
L104
L105
L152



1112.
L104
L106
L152



1113.
L104
L107
L152



1114.
L104
L108
L152



1115.
L104
L109
L152



1116.
L104
L110
L152



1117.
L104
L111
L152



1118.
L104
L112
L152



1119.
L104
L113
L152



1120.
L104
L114
L152



1121.
L104
L115
L152



1122.
L104
L116
L152



1123.
L104
L117
L152



1124.
L104
L118
L152



1125.
L104
L119
L152



1126.
L104
L130
L152



1127.
L104
L131
L152



1128.
L104
L132
L152



1129.
L104
L133
L152



1130.
L104
L134
L152



1131.
L104
L140
L152



1132.
L104
L141
L152



1133.
L104
L159
L152



1134.
L104
L160
L152



1135.
L104
L105
L164



1136.
L104
L106
L164



1137.
L104
L107
L164



1138.
L104
L108
L164



1139.
L104
L109
L164



1140.
L104
L110
L164



1141.
L104
L111
L164



1142.
L104
L112
L164



1143.
L104
L113
L164



1144.
L104
L114
L164



1145.
L104
L115
L164



1146.
L104
L116
L164



1147.
L104
L117
L164



1148.
L104
L118
L164



1149.
L104
L119
L164



1150.
L104
L130
L164



1151.
L104
L131
L164



1152.
L104
L132
L164



1153.
L104
L133
L164



1154.
L104
L134
L164



1155.
L104
L140
L164



1156.
L104
L141
L164



1157.
L104
L159
L164



1158.
L104
L160
L164



1159.
L104
L105
L165



1160.
L104
L106
L165



1161.
L104
L107
L165



1162.
L104
L108
L165



1163.
L104
L109
L165



1164.
L104
L110
L165



1165.
L104
L111
L165



1166.
L104
L112
L165



1167.
L104
L113
L165



1168.
L104
L114
L165



1169.
L104
L115
L165



1170.
L104
L116
L165



1171.
L104
L117
L165



1172.
L104
L118
L165



1173.
L104
L119
L165



1174.
L104
L130
L165



1175.
L104
L131
L165



1176.
L104
L132
L165



1177.
L104
L133
L165



1178.
L104
L134
L165



1179.
L104
L140
L165



1180.
L104
L141
L165



1181.
L104
L159
L165



1182.
L104
L160
L165



1183.
L104
L105
L166



1184.
L104
L106
L166



1185.
L104
L107
L166



1186.
L104
L108
L166



1187.
L104
L109
L166



1188.
L104
L110
L166



1189.
L104
L111
L166



1190.
L104
L112
L166



1191.
L104
L113
L166



1192.
L104
L114
L166



1193.
L104
L115
L166



1194.
L104
L116
L166



1195.
L104
L117
L166



1196.
L104
L118
L166



1197.
L104
L119
L166



1198.
L104
L130
L166



1199.
L104
L131
L166



1200.
L104
L132
L166



1201.
L104
L133
L166



1202.
L104
L134
L166



1203.
L104
L140
L166



1204.
L104
L141
L166



1205.
L104
L159
L166



1206.
L104
L160
L166



1207.
L104
L105
L170



1208.
L104
L106
L170



1209.
L104
L107
L170



1210.
L104
L108
L170



1211.
L104
L109
L170



1212.
L104
L110
L170



1213.
L104
L111
L170



1214.
L104
L112
L170



1215.
L104
L113
L170



1216.
L104
L114
L170



1217.
L104
L115
L170



1218.
L104
L116
L170



1219.
L104
L117
L170



1220.
L104
L118
L170



1221.
L104
L119
L170



1222.
L104
L130
L170



1223.
L104
L131
L170



1224.
L104
L132
L170



1225.
L104
L133
L170



1226.
L104
L134
L170



1227.
L104
L140
L170



1228.
L104
L141
L170



1229.
L104
L159
L170



1230.
L104
L160
L170



1231.
L104
L105
L174



1232.
L104
L106
L174



1233.
L104
L107
L174



1234.
L104
L108
L174



1235.
L104
L109
L174



1236.
L104
L110
L174



1237.
L104
L111
L174



1238.
L104
L112
L174



1239.
L104
L113
L174



1240.
L104
L114
L174



1241.
L104
L115
L174



1242.
L104
L116
L174



1243.
L104
L117
L174



1244.
L104
L118
L174



1245.
L104
L119
L174



1246.
L104
L130
L174



1247.
L104
L131
L174



1248.
L104
L132
L174



1249.
L104
L133
L174



1250.
L104
L134
L174



1251.
L104
L140
L174



1252.
L104
L141
L174



1253.
L104
L159
L174



1254.
L104
L160
L174



1255.
L104
L105
L176



1256.
L104
L106
L176



1257.
L104
L107
L176



1258.
L104
L108
L176



1259.
L104
L109
L176



1260.
L104
L110
L176



1261.
L104
L111
L176



1262.
L104
L112
L176



1263.
L104
L113
L176



1264.
L104
L114
L176



1265.
L104
L115
L176



1266.
L104
L116
L176



1267.
L104
L117
L176



1268.
L104
L118
L176



1269.
L104
L119
L176



1270.
L104
L130
L176



1271.
L104
L131
L176



1272.
L104
L132
L176



1273.
L104
L133
L176



1274.
L104
L134
L176



1275.
L104
L140
L176



1276.
L104
L141
L176



1277.
L104
L159
L176



1278.
L104
L160
L176



1279.
L104
L105
L179



1280.
L104
L106
L179



1281.
L104
L107
L179



1282.
L104
L108
L179



1283.
L104
L109
L179



1284.
L104
L110
L179



1285.
L104
L111
L179



1286.
L104
L112
L179



1287.
L104
L113
L179



1288.
L104
L114
L179



1289.
L104
L115
L179



1290.
L104
L116
L179



1291.
L104
L117
L179



1292.
L104
L118
L179



1293.
L104
L119
L179



1294.
L104
L130
L179



1295.
L104
L131
L179



1296.
L104
L132
L179



1297.
L104
L133
L179



1298.
L104
L134
L179



1299.
L104
L140
L179



1300.
L104
L141
L179



1301.
L104
L159
L179



1302.
L104
L160
L179



1303.
L104
L105
L180



1304.
L104
L106
L180



1305.
L104
L107
L180



1306.
L104
L108
L180



1307.
L104
L109
L180



1308.
L104
L110
L180



1309.
L104
L111
L180



1310.
L104
L112
L180



1311.
L104
L113
L180



1312.
L104
L114
L180



1313.
L104
L115
L180



1314.
L104
L116
L180



1315.
L104
L117
L180



1316.
L104
L118
L180



1317.
L104
L119
L180



1318.
L104
L130
L180



1319.
L104
L131
L180



1320.
L104
L132
L180



1321.
L104
L133
L180



1322.
L104
L134
L180



1323.
L104
L140
L180



1324.
L104
L141
L180



1325.
L104
L159
L180



1326.
L104
L160
L180



1327.
L105
L106
L144



1328.
L105
L107
L144



1329.
L105
L108
L144



1330.
L105
L109
L144



1331.
L105
L110
L144



1332.
L105
L111
L144



1333.
L105
L112
L144



1334.
L105
L113
L144



1335.
L105
L114
L144



1336.
L105
L115
L144



1337.
L105
L116
L144



1338.
L105
L117
L144



1339.
L105
L118
L144



1340.
L105
L119
L144



1341.
L105
L130
L144



1342.
L105
L131
L144



1343.
L105
L132
L144



1344.
L105
L133
L144



1345.
L105
L134
L144



1346.
L105
L140
L144



1347.
L105
L141
L144



1348.
L105
L159
L144



1349.
L105
L160
L144



1350.
L105
L106
L145



1351.
L105
L107
L145



1352.
L105
L108
L145



1353.
L105
L109
L145



1354.
L105
L110
L145



1355.
L105
L111
L145



1356.
L105
L112
L145



1357.
L105
L113
L145



1358.
L105
L114
L145



1359.
L105
L115
L145



1360.
L105
L116
L145



1361.
L105
L117
L145



1362.
L105
L118
L145



1363.
L105
L119
L145



1364.
L105
L130
L145



1365.
L105
L131
L145



1366.
L105
L132
L145



1367.
L105
L133
L145



1368.
L105
L134
L145



1369.
L105
L140
L145



1370.
L105
L141
L145



1371.
L105
L159
L145



1372.
L105
L160
L145



1373.
L105
L106
L147



1374.
L105
L107
L147



1375.
L105
L108
L147



1376.
L105
L109
L147



1377.
L105
L110
L147



1378.
L105
L111
L147



1379.
L105
L112
L147



1380.
L105
L113
L147



1381.
L105
L114
L147



1382.
L105
L115
L147



1383.
L105
L116
L147



1384.
L105
L117
L147



1385.
L105
L118
L147



1386.
L105
L119
L147



1387.
L105
L130
L147



1388.
L105
L131
L147



1389.
L105
L132
L147



1390.
L105
L133
L147



1391.
L105
L134
L147



1392.
L105
L140
L147



1393.
L105
L141
L147



1394.
L105
L159
L147



1395.
L105
L160
L147



1396.
L105
L106
L149



1397.
L105
L107
L149



1398.
L105
L108
L149



1399.
L105
L109
L149



1400.
L105
L110
L149



1401.
L105
L111
L149



1402.
L105
L112
L149



1403.
L105
L113
L149



1404.
L105
L114
L149



1405.
L105
L115
L149



1406.
L105
L116
L149



1407.
L105
L117
L149



1408.
L105
L118
L149



1409.
L105
L119
L149



1410.
L105
L130
L149



1411.
L105
L131
L149



1412.
L105
L132
L149



1413.
L105
L133
L149



1414.
L105
L134
L149



1415.
L105
L140
L149



1416.
L105
L141
L149



1417.
L105
L159
L149



1418.
L105
L160
L149



1419.
L105
L106
L152



1420.
L105
L107
L152



1421.
L105
L108
L152



1422.
L105
L109
L152



1423.
L105
L110
L152



1424.
L105
L111
L152



1425.
L105
L112
L152



1426.
L105
L113
L152



1427.
L105
L114
L152



1428.
L105
L115
L152



1429.
L105
L116
L152



1430.
L105
L117
L152



1431.
L105
L118
L152



1432.
L105
L119
L152



1433.
L105
L130
L152



1434.
L105
L131
L152



1435.
L105
L132
L152



1436.
L105
L133
L152



1437.
L105
L134
L152



1438.
L105
L140
L152



1439.
L105
L141
L152



1440.
L105
L159
L152



1441.
L105
L160
L152



1442.
L105
L106
L164



1443.
L105
L107
L164



1444.
L105
L108
L164



1445.
L105
L109
L164



1446.
L105
L110
L164



1447.
L105
L111
L164



1448.
L105
L112
L164



1449.
L105
L113
L164



1450.
L105
L114
L164



1451.
L105
L115
L164



1452.
L105
L116
L164



1453.
L105
L117
L164



1454.
L105
L118
L164



1455.
L105
L119
L164



1456.
L105
L130
L164



1457.
L105
L131
L164



1458.
L105
L132
L164



1459.
L105
L133
L164



1460.
L105
L134
L164



1461.
L105
L140
L164



1462.
L105
L141
L164



1463.
L105
L159
L164



1464.
L105
L160
L164



1465.
L105
L106
L165



1466.
L105
L107
L165



1467.
L105
L108
L165



1468.
L105
L109
L165



1469.
L105
L110
L165



1470.
L105
L111
L165



1471.
L105
L112
L165



1472.
L105
L113
L165



1473.
L105
L114
L165



1474.
L105
L115
L165



1475.
L105
L116
L165



1476.
L105
L117
L165



1477.
L105
L118
L165



1478.
L105
L119
L165



1479.
L105
L130
L165



1480.
L105
L131
L165



1481.
L105
L132
L165



1482.
L105
L133
L165



1483.
L105
L134
L165



1484.
L105
L140
L165



1485.
L105
L141
L165



1486.
L105
L159
L165



1487.
L105
L160
L165



1488.
L105
L106
L166



1489.
L105
L107
L166



1490.
L105
L108
L166



1491.
L105
L109
L166



1492.
L105
L110
L166



1493.
L105
L111
L166



1494.
L105
L112
L166



1495.
L105
L113
L166



1496.
L105
L114
L166



1497.
L105
L115
L166



1498.
L105
L116
L166



1499.
L105
L117
L166



1500.
L105
L118
L166



1501.
L105
L119
L166



1502.
L105
L130
L166



1503.
L105
L131
L166



1504.
L105
L132
L166



1505.
L105
L133
L166



1506.
L105
L134
L166



1507.
L105
L140
L166



1508.
L105
L141
L166



1509.
L105
L159
L166



1510.
L105
L160
L166



1511.
L105
L106
L170



1512.
L105
L107
L170



1513.
L105
L108
L170



1514.
L105
L109
L170



1515.
L105
L110
L170



1516.
L105
L111
L170



1517.
L105
L112
L170



1518.
L105
L113
L170



1519.
L105
L114
L170



1520.
L105
L115
L170



1521.
L105
L116
L170



1522.
L105
L117
L170



1523.
L105
L118
L170



1524.
L105
L119
L170



1525.
L105
L130
L170



1526.
L105
L131
L170



1527.
L105
L132
L170



1528.
L105
L133
L170



1529.
L105
L134
L170



1530.
L105
L140
L170



1531.
L105
L141
L170



1532.
L105
L159
L170



1533.
L105
L160
L170



1534.
L105
L106
L174



1535.
L105
L107
L174



1536.
L105
L108
L174



1537.
L105
L109
L174



1538.
L105
L110
L174



1539.
L105
L111
L174



1540.
L105
L112
L174



1541.
L105
L113
L174



1542.
L105
L114
L174



1543.
L105
L115
L174



1544.
L105
L116
L174



1545.
L105
L117
L174



1546.
L105
L118
L174



1547.
L105
L119
L174



1548.
L105
L130
L174



1549.
L105
L131
L174



1550.
L105
L132
L174



1551.
L105
L133
L174



1552.
L105
L134
L174



1553.
L105
L140
L174



1554.
L105
L141
L174



1555.
L105
L159
L174



1556.
L105
L160
L174



1557.
L105
L106
L176



1558.
L105
L107
L176



1559.
L105
L108
L176



1560.
L105
L109
L176



1561.
L105
L110
L176



1562.
L105
L111
L176



1563.
L105
L112
L176



1564.
L105
L113
L176



1565.
L105
L114
L176



1566.
L105
L115
L176



1567.
L105
L116
L176



1568.
L105
L117
L176



1569.
L105
L118
L176



1570.
L105
L119
L176



1571.
L105
L130
L176



1572.
L105
L131
L176



1573.
L105
L132
L176



1574.
L105
L133
L176



1575.
L105
L134
L176



1576.
L105
L140
L176



1577.
L105
L141
L176



1578.
L105
L159
L176



1579.
L105
L160
L176



1580.
L105
L106
L179



1581.
L105
L107
L179



1582.
L105
L108
L179



1583.
L105
L109
L179



1584.
L105
L110
L179



1585.
L105
L111
L179



1586.
L105
L112
L179



1587.
L105
L113
L179



1588.
L105
L114
L179



1589.
L105
L115
L179



1590.
L105
L116
L179



1591.
L105
L117
L179



1592.
L105
L118
L179



1593.
L105
L119
L179



1594.
L105
L130
L179



1595.
L105
L131
L179



1596.
L105
L132
L179



1597.
L105
L133
L179



1598.
L105
L134
L179



1599.
L105
L140
L179



1600.
L105
L141
L179



1601.
L105
L159
L179



1602.
L105
L160
L179



1603.
L105
L106
L180



1604.
L105
L107
L180



1605.
L105
L108
L180



1606.
L105
L109
L180



1607.
L105
L110
L180



1608.
L105
L111
L180



1609.
L105
L112
L180



1610.
L105
L113
L180



1611.
L105
L114
L180



1612.
L105
L115
L180



1613.
L105
L116
L180



1614.
L105
L117
L180



1615.
L105
L118
L180



1616.
L105
L119
L180



1617.
L105
L130
L180



1618.
L105
L131
L180



1619.
L105
L132
L180



1620.
L105
L133
L180



1621.
L105
L134
L180



1622.
L105
L140
L180



1623.
L105
L141
L180



1624.
L105
L159
L180



1625.
L105
L160
L180



1626.
L106
L107
L144



1627.
L106
L108
L144



1628.
L106
L109
L144



1629.
L106
L110
L144



1630.
L106
L111
L144



1631.
L106
L112
L144



1632.
L106
L113
L144



1633.
L106
L114
L144



1634.
L106
L115
L144



1635.
L106
L116
L144



1636.
L106
L117
L144



1637.
L106
L118
L144



1638.
L106
L119
L144



1639.
L106
L130
L144



1640.
L106
L131
L144



1641.
L106
L132
L144



1642.
L106
L133
L144



1643.
L106
L134
L144



1644.
L106
L140
L144



1645.
L106
L141
L144



1646.
L106
L159
L144



1647.
L106
L160
L144



1648.
L106
L107
L145



1649.
L106
L108
L145



1650.
L106
L109
L145



1651.
L106
L110
L145



1652.
L106
L111
L145



1653.
L106
L112
L145



1654.
L106
L113
L145



1655.
L106
L114
L145



1656.
L106
L115
L145



1657.
L106
L116
L145



1658.
L106
L117
L145



1659.
L106
L118
L145



1660.
L106
L119
L145



1661.
L106
L130
L145



1662.
L106
L131
L145



1663.
L106
L132
L145



1664.
L106
L133
L145



1665.
L106
L134
L145



1666.
L106
L140
L145



1667.
L106
L141
L145



1668.
L106
L159
L145



1669.
L106
L160
L145



1670.
L106
L107
L147



1671.
L106
L108
L147



1672.
L106
L109
L147



1673.
L106
L110
L147



1674.
L106
L111
L147



1675.
L106
L112
L147



1676.
L106
L113
L147



1677.
L106
L114
L147



1678.
L106
L115
L147



1679.
L106
L116
L147



1680.
L106
L117
L147



1681.
L106
L118
L147



1682.
L106
L119
L147



1683.
L106
L130
L147



1684.
L106
L131
L147



1685.
L106
L132
L147



1686.
L106
L133
L147



1687.
L106
L134
L147



1688.
L106
L140
L147



1689.
L106
L141
L147



1690.
L106
L159
L147



1691.
L106
L160
L147



1692.
L106
L107
L149



1693.
L106
L108
L149



1694.
L106
L109
L149



1695.
L106
L110
L149



1696.
L106
L111
L149



1697.
L106
L112
L149



1698.
L106
L113
L149



1699.
L106
L114
L149



1700.
L106
L115
L149



1701.
L106
L116
L149



1702.
L106
L117
L149



1703.
L106
L118
L149



1704.
L106
L119
L149



1705.
L106
L130
L149



1706.
L106
L131
L149



1707.
L106
L132
L149



1708.
L106
L133
L149



1709.
L106
L134
L149



1710.
L106
L140
L149



1711.
L106
L141
L149



1712.
L106
L159
L149



1713.
L106
L160
L149



1714.
L106
L107
L152



1715.
L106
L108
L152



1716.
L106
L109
L152



1717.
L106
L110
L152



1718.
L106
L111
L152



1719.
L106
L112
L152



1720.
L106
L113
L152



1721.
L106
L114
L152



1722.
L106
L115
L152



1723.
L106
L116
L152



1724.
L106
L117
L152



1725.
L106
L118
L152



1726.
L106
L119
L152



1727.
L106
L130
L152



1728.
L106
L131
L152



1729.
L106
L132
L152



1730.
L106
L133
L152



1731.
L106
L134
L152



1732.
L106
L140
L152



1733.
L106
L141
L152



1734.
L106
L159
L152



1735.
L106
L160
L152



1736.
L106
L107
L164



1737.
L106
L108
L164



1738.
L106
L109
L164



1739.
L106
L110
L164



1740.
L106
L111
L164



1741.
L106
L112
L164



1742.
L106
L113
L164



1743.
L106
L114
L164



1744.
L106
L115
L164



1745.
L106
L116
L164



1746.
L106
L117
L164



1747.
L106
L118
L164



1748.
L106
L119
L164



1749.
L106
L130
L164



1750.
L106
L131
L164



1751.
L106
L132
L164



1752.
L106
L133
L164



1753.
L106
L134
L164



1754.
L106
L140
L164



1755.
L106
L141
L164



1756.
L106
L159
L164



1757.
L106
L160
L164



1758.
L106
L107
L165



1759.
L106
L108
L165



1760.
L106
L109
L165



1761.
L106
L110
L165



1762.
L106
L111
L165



1763.
L106
L112
L165



1764.
L106
L113
L165



1765.
L106
L114
L165



1766.
L106
L115
L165



1767.
L106
L116
L165



1768.
L106
L117
L165



1769.
L106
L118
L165



1770.
L106
L119
L165



1771.
L106
L130
L165



1772.
L106
L131
L165



1773.
L106
L132
L165



1774.
L106
L133
L165



1775.
L106
L134
L165



1776.
L106
L140
L165



1777.
L106
L141
L165



1778.
L106
L159
L165



1779.
L106
L160
L165



1780.
L106
L107
L166



1781.
L106
L108
L166



1782.
L106
L109
L166



1783.
L106
L110
L166



1784.
L106
L111
L166



1785.
L106
L112
L166



1786.
L106
L113
L166



1787.
L106
L114
L166



1788.
L106
L115
L166



1789.
L106
L116
L166



1790.
L106
L117
L166



1791.
L106
L118
L166



1792.
L106
L119
L166



1793.
L106
L130
L166



1794.
L106
L131
L166



1795.
L106
L132
L166



1796.
L106
L133
L166



1797.
L106
L134
L166



1798.
L106
L140
L166



1799.
L106
L141
L166



1800.
L106
L159
L166



1801.
L106
L160
L166



1802.
L106
L107
L170



1803.
L106
L108
L170



1804.
L106
L109
L170



1805.
L106
L110
L170



1806.
L106
L111
L170



1807.
L106
L112
L170



1808.
L106
L113
L170



1809.
L106
L114
L170



1810.
L106
L115
L170



1811.
L106
L116
L170



1812.
L106
L117
L170



1813.
L106
L118
L170



1814.
L106
L119
L170



1815.
L106
L130
L170



1816.
L106
L131
L170



1817.
L106
L132
L170



1818.
L106
L133
L170



1819.
L106
L134
L170



1820.
L106
L140
L170



1821.
L106
L141
L170



1822.
L106
L159
L170



1823.
L106
L160
L170



1824.
L106
L107
L174



1825.
L106
L108
L174



1826.
L106
L109
L174



1827.
L106
L110
L174



1828.
L106
L111
L174



1829.
L106
L112
L174



1830.
L106
L113
L174



1831.
L106
L114
L174



1832.
L106
L115
L174



1833.
L106
L116
L174



1834.
L106
L117
L174



1835.
L106
L118
L174



1836.
L106
L119
L174



1837.
L106
L130
L174



1838.
L106
L131
L174



1839.
L106
L132
L174



1840.
L106
L133
L174



1841.
L106
L134
L174



1842.
L106
L140
L174



1843.
L106
L141
L174



1844.
L106
L159
L174



1845.
L106
L160
L174



1846.
L106
L107
L176



1847.
L106
L108
L176



1848.
L106
L109
L176



1849.
L106
L110
L176



1850.
L106
L111
L176



1851.
L106
L112
L176



1852.
L106
L113
L176



1853.
L106
L114
L176



1854.
L106
L115
L176



1855.
L106
L116
L176



1856.
L106
L117
L176



1857.
L106
L118
L176



1858.
L106
L119
L176



1859.
L106
L130
L176



1860.
L106
L131
L176



1861.
L106
L132
L176



1862.
L106
L133
L176



1863.
L106
L134
L176



1864.
L106
L140
L176



1865.
L106
L141
L176



1866.
L106
L159
L176



1867.
L106
L160
L176



1868.
L106
L107
L179



1869.
L106
L108
L179



1870.
L106
L109
L179



1871.
L106
L110
L179



1872.
L106
L111
L179



1873.
L106
L112
L179



1874.
L106
L113
L179



1875.
L106
L114
L179



1876.
L106
L115
L179



1877.
L106
L116
L179



1878.
L106
L117
L179



1879.
L106
L118
L179



1880.
L106
L119
L179



1881.
L106
L130
L179



1882.
L106
L131
L179



1883.
L106
L132
L179



1884.
L106
L133
L179



1885.
L106
L134
L179



1886.
L106
L140
L179



1887.
L106
L141
L179



1888.
L106
L159
L179



1889.
L106
L160
L179



1890.
L106
L107
L180



1891.
L106
L108
L180



1892.
L106
L109
L180



1893.
L106
L110
L180



1894.
L106
L111
L180



1895.
L106
L112
L180



1896.
L106
L113
L180



1897.
L106
L114
L180



1898.
L106
L115
L180



1899.
L106
L116
L180



1900.
L106
L117
L180



1901.
L106
L118
L180



1902.
L106
L119
L180



1903.
L106
L130
L180



1904.
L106
L131
L180



1905.
L106
L132
L180



1906.
L106
L133
L180



1907.
L106
L134
L180



1908.
L106
L140
L180



1909.
L106
L141
L180



1910.
L106
L159
L180



1911.
L106
L160
L180



1912.
L107
L108
L144



1913.
L107
L109
L144



1914.
L107
L110
L144



1915.
L107
L111
L144



1916.
L107
L112
L144



1917.
L107
L113
L144



1918.
L107
L114
L144



1919.
L107
L115
L144



1920.
L107
L116
L144



1921.
L107
L117
L144



1922.
L107
L118
L144



1923.
L107
L119
L144



1924.
L107
L130
L144



1925.
L107
L131
L144



1926.
L107
L132
L144



1927.
L107
L133
L144



1928.
L107
L134
L144



1929.
L107
L140
L144



1930.
L107
L141
L144



1931.
L107
L159
L144



1932.
L107
L160
L144



1933.
L107
L108
L145



1934.
L107
L109
L145



1935.
L107
L110
L145



1936.
L107
L111
L145



1937.
L107
L112
L145



1938.
L107
L113
L145



1939.
L107
L114
L145



1940.
L107
L115
L145



1941.
L107
L116
L145



1942.
L107
L117
L145



1943.
L107
L118
L145



1944.
L107
L119
L145



1945.
L107
L130
L145



1946.
L107
L131
L145



1947.
L107
L132
L145



1948.
L107
L133
L145



1949.
L107
L134
L145



1950.
L107
L140
L145



1951.
L107
L141
L145



1952.
L107
L159
L145



1953.
L107
L160
L145



1954.
L107
L108
L147



1955.
L107
L109
L147



1956.
L107
L110
L147



1957.
L107
L111
L147



1958.
L107
L112
L147



1959.
L107
L113
L147



1960.
L107
L114
L147



1961.
L107
L115
L147



1962.
L107
L116
L147



1963.
L107
L117
L147



1964.
L107
L118
L147



1965.
L107
L119
L147



1966.
L107
L130
L147



1967.
L107
L131
L147



1968.
L107
L132
L147



1969.
L107
L133
L147



1970.
L107
L134
L147



1971.
L107
L140
L147



1972.
L107
L141
L147



1973.
L107
L159
L147



1974.
L107
L160
L147



1975.
L107
L108
L149



1976.
L107
L109
L149



1977.
L107
L110
L149



1978.
L107
L111
L149



1979.
L107
L112
L149



1980.
L107
L113
L149



1981.
L107
L114
L149



1982.
L107
L115
L149



1983.
L107
L116
L149



1984.
L107
L117
L149



1985.
L107
L118
L149



1986.
L107
L119
L149



1987.
L107
L130
L149



1988.
L107
L131
L149



1989.
L107
L132
L149



1990.
L107
L133
L149



1991.
L107
L134
L149



1992.
L107
L140
L149



1993.
L107
L141
L149



1994.
L107
L159
L149



1995.
L107
L160
L149



1996.
L107
L108
L152



1997.
L107
L109
L152



1998.
L107
L110
L152



1999.
L107
L111
L152



2000.
L107
L112
L152



2001.
L107
L113
L152



2002.
L107
L114
L152



2003.
L107
L115
L152



2004.
L107
L116
L152



2005.
L107
L117
L152



2006.
L107
L118
L152



2007.
L107
L119
L152



2008.
L107
L130
L152



2009.
L107
L131
L152



2010.
L107
L132
L152



2011.
L107
L133
L152



2012.
L107
L134
L152



2013.
L107
L140
L152



2014.
L107
L141
L152



2015.
L107
L159
L152



2016.
L107
L160
L152



2017.
L107
L108
L164



2018.
L107
L109
L164



2019.
L107
L110
L164



2020.
L107
L111
L164



2021.
L107
L112
L164



2022.
L107
L113
L164



2023.
L107
L114
L164



2024.
L107
L115
L164



2025.
L107
L116
L164



2026.
L107
L117
L164



2027.
L107
L118
L164



2028.
L107
L119
L164



2029.
L107
L130
L164



2030.
L107
L131
L164



2031.
L107
L132
L164



2032.
L107
1:33
L164



2033.
L107
L134
L164



2034.
L107
L140
L164



2035.
L107
L141
L164



2036.
L107
L159
L164



2037.
L107
L160
L164



2038.
L107
L108
L165



2039.
L107
L109
L165



2040.
L107
L110
L165



2041.
L107
L111
L165



2042.
L107
L112
L165



2043.
L107
L113
L165



2044.
L107
L114
L165



2045.
L107
L115
L165



2046.
L107
L116
L165



2047.
L107
L117
L165



2048.
L107
L118
L165



2049.
L107
L119
L165



2050.
L107
L130
L165



2051.
L107
L131
L165



2052.
L107
L132
L165



2053.
L107
L133
L165



2054.
L107
L134
L165



2055.
L107
L140
L165



2056.
L107
L141
L165



2057.
L107
L159
L165



2058.
L107
L160
L165



2059.
L107
L108
L166



2060.
L107
L109
L166



2061.
L107
L110
L166



2062.
L107
L111
L166



2063.
L107
L112
L166



2064.
L107
L113
L166



2065.
L107
L114
L166



2066.
L107
L115
L166



2067.
L107
L116
L166



2068.
L107
L117
L166



2069.
L107
L118
L166



2070.
L107
L119
L166



2071.
L107
L130
L166



2072.
L107
L131
L166



2073.
L107
L132
L166



2074.
L107
L133
L166



2075.
L107
L134
L166



2076.
L107
L140
L166



2077.
L107
L141
L166



2078.
L107
L159
L166



2079.
L107
L160
L166



2080.
L107
L108
L170



2081.
L107
L109
L170



2082.
L107
L110
L170



2083.
L107
L111
L170



2084.
L107
L112
L170



2085.
L107
L113
L170



2086.
L107
L114
L170



2087.
L107
L115
L170



2088.
L107
L116
L170



2089.
L107
L117
L170



2090.
L107
L118
L170



2091.
L107
L119
L170



2092.
L107
L130
L170



2093.
L107
L131
L170



2094.
L107
L132
L170



2095.
L107
L133
L170



2096.
L107
L134
L170



2097.
L107
L140
L170



2098.
L107
L141
L170



2099.
L107
L159
L170



2100.
L107
L160
L170



2101.
L107
L108
L174



2102.
L107
L109
L174



2103.
L107
L110
L174



2104.
L107
L111
L174



2105.
L107
L112
L174



2106.
L107
L113
L174



2107.
L107
L114
L174



2108.
L107
L115
L174



2109.
L107
L116
L174



2110.
L107
L117
L174



2111.
L107
L118
L174



2112.
L107
L119
L174



2113.
L107
L130
L174



2114.
L107
L131
L174



2115.
L107
L132
L174



2116.
L107
L133
L174



2117.
L107
L134
L174



2118.
L107
L140
L174



2119.
L107
L141
L174



2120.
L107
L159
L174



2121.
L107
L160
L174



2122.
L107
L108
L176



2123.
L107
L109
L176



2124.
L107
L110
L176



2125.
L107
L111
L176



2126.
L107
L112
L176



2127.
L107
L113
L176



2128.
L107
L114
L176



2129.
L107
L115
L176



2130.
L107
L116
L176



2131.
L107
L117
L176



2132.
L107
L118
L176



2133.
L107
L119
L176



2134.
L107
L130
L176



2135.
L107
L131
L176



2136.
L107
L132
L176



2137.
L107
L133
L176



2138.
L107
L134
L176



2139.
L107
L140
L176



2140.
L107
L141
L176



2141.
L107
L159
L176



2142.
L107
L160
L176



2143.
L107
L108
L179



2144.
L107
L109
L179



2145.
L107
L110
L179



2146.
L107
L111
L179



2147.
L107
L112
L179



2148.
L107
L113
L179



2149.
L107
L114
L179



2150.
L107
L115
L179



2151.
L107
L116
L179



2152.
L107
L117
L179



2153.
L107
L118
L179



2154.
L107
L119
L179



2155.
L107
L130
L179



2156.
L107
L131
L179



2157.
L107
L132
L179



2158.
L107
L133
L179



2159.
L107
L134
L179



2160.
L107
L140
L179



2161.
L107
L141
L179



2162.
L107
L159
L179



2163.
L107
L160
L179



2164.
L107
L108
L180



2165.
L107
L109
L180



2166.
L107
L110
L180



2167.
L107
L111
L180



2168.
L107
L112
L180



2169.
L107
L113
L180



2170.
L107
L114
L180



2171.
L107
L115
L180



2172.
L107
L116
L180



2173.
L107
L117
L180



2174.
L107
L118
L180



2175.
L107
L119
L180



2176.
L107
L130
L180



2177.
L107
L131
L180



2178.
L107
L132
L180



2179.
L107
L133
L180



2180.
L107
L134
L180



2181.
L107
L140
L180



2182.
L107
L141
L180



2183.
L107
L159
L180



2184.
L107
L160
L180



2185.
L108
L109
L144



2186.
L108
L110
L144



2187.
L108
L111
L144



2188.
L108
L112
L144



2189.
L108
L113
L144



2190.
L108
L114
L144



2191.
L108
L115
L144



2192.
L108
L116
L144



2193.
L108
L117
L144



2194.
L108
L118
L144



2195.
L108
L119
L144



2196.
L108
L130
L144



2197.
L108
L131
L144



2198.
L108
L132
L144



2199.
L108
L133
L144



2200.
L108
L134
L144



2201.
L108
L140
L144



2202.
L108
L141
L144



2203.
L108
L159
L144



2204.
L108
L160
L144



2205.
L108
L109
L145



2206.
L108
L110
L145



2207.
L108
L111
L145



2208.
L108
L112
L145



2209.
L108
L113
L145



2210.
L108
L114
L145



2211.
L108
L115
L145



2212.
L108
L116
L145



2213.
L108
L117
L145



2214.
L108
L118
L145



2215.
L108
L119
L145



2216.
L108
L130
L145



2217.
L108
L131
L145



2218.
L108
L132
L145



2219.
L108
L133
L145



2220.
L108
L134
L145



2221.
L108
L140
L145



2222.
L108
L141
L145



2223.
L108
L159
L145



2224.
L108
L160
L145



2225.
L108
L109
L147



2226.
L108
L110
L147



2227.
L108
L111
L147



2228.
L108
L112
L147



2229.
L108
L113
L147



2230.
L108
L114
L147



2231.
L108
L115
L147



2232.
L108
L116
L147



2233.
L108
L117
L147



2234.
L108
L118
L147



2235.
L108
L119
L147



2236.
L108
L130
L147



2237.
L108
L131
L147



2238.
L108
L132
L147



2239.
L108
L133
L147



2240.
L108
L134
L147



2241.
L108
L140
L147



2242.
L108
L141
L147



2243.
L108
L159
L147



2244.
L108
L160
L147



2245.
L108
L109
L149



2246.
L108
L110
L149



2247.
L108
L111
L149



2248.
L108
L112
L149



2249.
L108
L113
L149



2250.
L108
L114
L149



2251.
L108
L115
L149



2252.
L108
L116
L149



2253.
L108
L117
L149



2254.
L108
L118
L149



2255.
L108
L119
L149



2256.
L108
L130
L149



2257.
L108
L131
L149



2258.
L108
L132
L149



2259.
L108
L133
L149



2260.
L108
L134
L149



2261.
L108
L140
L149



2262.
L118
L141
L149



2263.
L108
L159
L149



2264.
L108
L160
L149



2265.
L108
L109
L152



2266.
L108
L110
L152



2267.
L108
L111
L152



2268.
L108
L112
L152



2269.
L108
L113
L152



2270.
L108
L114
L152



2271.
L108
L115
L152



2272.
L108
L116
L152



2273.
L108
L117
L152



2274.
L108
L118
L152



2275.
L108
L119
L152



2276.
L108
L130
L152



2277.
L108
L131
L152



2278.
L108
L132
L152



2279.
L108
L133
L152



2280.
L108
L134
L152



2281.
L108
L140
L152



2282.
L108
L141
L152



2283.
L108
L159
L152



2284.
L108
L160
L152



2285.
L108
L109
L164



2286.
L108
L110
L164



2287.
L108
L111
L164



2288.
L108
L112
L164



2289.
L108
L113
L164



2290.
L108
L114
L164



2291.
L108
L115
L164



2292.
L108
L116
L164



2293.
L108
L117
L164



2294.
L108
L118
L164



2295.
L108
L119
L164



2296.
L108
L130
L164



2297.
L108
L131
L164



2298.
L108
L132
L164



2299.
L108
L133
L164



2300.
L108
L134
L164



2301.
L108
L140
L164



2302.
L108
L141
L164



2303.
L108
L159
L164



2304.
L108
L160
L164



2305.
L108
L109
L165



2306.
L108
L110
L165



2307.
L108
L111
L165



2308.
L108
L112
L165



2309.
L108
L113
L165



2310.
L108
L114
L165



2311.
L108
L115
L165



2312.
L108
L116
L165



2313.
L108
L117
L165



2314.
L108
L118
L165



2315.
L108
L119
L165



2316.
L108
L130
L165



2317.
L108
L131
L165



2318.
L108
L132
L165



2319.
L108
L133
L165



2320.
L108
L134
L165



2321.
L108
L140
L165



2322.
L108
L141
L165



2323.
L108
L159
L165



2324.
L108
L160
L165



2325.
L108
L109
L166



2326.
L108
L110
L166



2327.
L108
L111
L166



2328.
L108
L112
L166



2329.
L108
L113
L166



2330.
L108
L114
L166



2331.
L108
L115
L166



2332.
L108
L116
L166



2333.
L108
L117
L166



2334.
L108
L118
L166



2335.
L108
L119
L166



2336.
L108
L130
L166



2337.
L108
L131
L166



2338.
L108
L132
L166



2339.
L108
L133
L166



2340.
L108
L134
L166



2341.
L108
L140
L166



2342.
L108
L141
L166



2343.
L108
L159
L166



2344.
L108
L160
L166



2345.
L108
L109
L170



2346.
L108
L110
L170



2347.
L108
L111
L170



2348.
L108
L112
L170



2349.
L108
L113
L170



2350.
L108
L114
L170



2351.
L108
L115
L170



2352.
L108
L116
L170



2353.
L108
L117
L170



2354.
L108
L118
L170



2355.
L108
L119
L170



2356.
L108
L130
L170



2357.
L108
L131
L170



2358.
L108
L132
L170



2359.
L108
L133
L170



2360.
L108
L134
L170



2361.
L108
L140
L170



2362.
L108
L141
L170



2363.
L108
L159
L170



2364.
L108
L160
L170



2365.
L108
L109
L174



2366.
L108
L110
L174



2367.
L108
L111
L174



2368.
L108
L112
L174



2369.
L108
L113
L174



2370.
L108
L114
L174



2371.
L108
L115
L174



2372.
L108
L116
L174



2373.
L108
L117
L174



2374.
L108
L118
L174



2375.
L108
L119
L174



2376.
L108
L130
L174



2377.
L108
L131
L174



2378.
L108
L132
L174



2379.
L108
L133
L174



2380.
L108
L134
L174



2381.
L108
L140
L174



2382.
L108
L141
L174



2383.
L108
L159
L174



2384.
L108
L160
L174



2385.
L108
L109
L176



2386.
L108
L110
L176



2387.
L108
L111
L176



2388.
L108
L112
L176



2389.
L108
L113
L176



2390.
L108
L114
L176



2391.
L108
L115
L176



2392.
L108
L116
L176



2393.
L108
L117
L176



2394.
L108
L118
L176



2395.
L108
L119
L176



2396.
L108
L130
L176



2397.
L108
L131
L176



2398.
L108
L132
L176



2399.
L108
L133
L176



2400.
L108
L134
L176



2401.
L108
L140
L176



2402.
L108
L141
L176



2403.
L108
L159
L176



2404.
L108
L160
L176



2405.
L108
L109
L179



2406.
L108
L110
L179



2407.
L108
L111
L179



2408.
L108
L112
L179



2409.
L108
L113
L179



2410.
L108
L114
L179



2411.
L108
L115
L179



2412.
L108
L116
L179



2413.
L108
L117
L179



2414.
L108
L118
L179



2415.
L108
L119
L179



2416.
L108
L130
L179



2417.
L108
L131
L179



2418.
L108
L132
L179



2419.
L108
L133
L179



2420.
L108
L134
L179



2421.
L108
L140
L179



2422.
L108
L141
L179



2423.
L108
L159
L179



2424.
L108
L160
L179



2425.
L108
L109
L180



2426.
L108
L110
L180



2427.
L108
L111
L180



2428.
L108
L112
L180



2429.
L108
L113
L180



2430.
L108
L114
L180



2431.
L108
L115
L180



2432.
L108
L116
L180



2433.
L108
L117
L180



2434.
L108
L118
L180



2435.
L108
L119
L180



2436.
L108
L130
L180



2437.
L108
L131
L180



2438.
L108
L132
L180



2439.
L108
L133
L180



2440.
L108
L134
L180



2441.
L108
L140
L180



2442.
L108
L141
L180



2443.
L108
L159
L180



2444.
L108
L160
L180



2445.
L109
L110
L144



2446.
L109
L111
L144



2447.
L109
L112
L144



2448.
L109
L113
L144



2449.
L109
L114
L144



2450.
L109
L115
L144



2451.
L109
L116
L144



2452.
L109
L117
L144



2453.
L109
L118
L144



2454.
L109
L119
L144



2455.
L109
L130
L144



2456.
L109
L131
L144



2457.
L109
L132
L144



2458.
L109
L133
L144



2459.
L109
L134
L144



2460.
L109
L140
L144



2461.
L109
L141
L144



2462.
L109
L159
L144



2463.
L109
L160
L144



2464.
L109
L110
L145



2465.
L109
L111
L145



2466.
L109
L112
L145



2467.
L109
L113
L145



2468.
L109
L114
L145



2469.
L109
L115
L145



2470.
L109
L116
L145



2471.
L109
L117
L145



2472.
L109
L118
L145



2473.
L109
L119
L145



2474.
L109
L130
L145



2475.
L109
L131
L145



2476.
L109
L132
L145



2477.
L109
L133
L145



2478.
L109
L134
L145



2479.
L109
L140
L145



2480.
L109
L141
L145



2481.
L109
L159
L145



2482.
L109
L160
L145



2483.
L109
L110
L147



2484.
L109
L111
L147



2485.
L109
L112
L147



2486.
L109
L113
L147



2487.
L109
L114
L147



2488.
L109
L115
L147



2489.
L109
L116
L147



2490.
L109
L117
L147



2491.
L109
L118
L147



2492.
L109
L119
L147



2493.
L109
L130
L147



2494.
L109
L131
L147



2495.
L109
L132
L147



2496.
L109
L133
L147



2497.
L109
L134
L147



2498.
L109
L140
L147



2499.
L109
L141
L147



2500.
L109
L159
L147



2501.
L109
L160
L147



2502.
L109
L110
L149



2503.
L109
L111
L149



2504.
L109
L112
L149



2505.
L109
L113
L149



2506.
L109
L114
L149



2507.
L109
L115
L149



2508.
L109
L116
L149



2509.
L109
L117
L149



2510.
L109
L118
L149



2511.
L109
L119
L149



2512.
L109
L130
L149



2513.
L109
L131
L149



2514.
L109
L132
L149



2515.
L109
L133
L149



2516.
L109
L134
L149



2517.
L109
L140
L149



2518.
L109
L141
L149



2519.
L109
L159
L149



2520.
L109
L160
L149



2521.
L109
L110
L152



2522.
L109
L111
L152



2523.
L109
L112
L152



2524.
L109
L113
L152



2525.
L109
L114
L152



2526.
L109
L115
L152



2527.
L109
L116
L152



2528.
L109
L117
L152



2529.
L109
L118
L152



2530.
L109
L119
L152



2531.
L109
L130
L152



2532.
L109
L131
L152



2533.
L109
L132
L152



2534.
L109
L133
L152



2535.
L109
L134
L152



2536.
L109
L140
L152



2537.
L109
L141
L152



2538.
L109
L159
L152



2539.
L109
L160
L152



2540.
L109
L110
L164



2541.
L109
L111
L164



2542.
L109
L112
L164



2543.
L109
L113
L164



2544.
L109
L114
L164



2545.
L109
L115
L164



2546.
L109
L116
L164



2547.
L109
L117
L164



2548.
L109
L118
L164



2549.
L109
L119
L164



2550.
L109
L130
L164



2551.
L109
L131
L164



2552.
L109
L132
L164



2553.
L109
L133
L164



2554.
L109
L134
L164



2555.
L109
L140
L164



2556.
L109
L141
L164



2557.
L109
L159
L164



2558.
L109
L160
L164



2559.
L109
L110
L165



2560.
L109
L111
L165



2561.
L109
L112
L165



2562.
L109
L113
L165



2563.
L109
L114
L165



2564.
L109
L115
L165



2565.
L109
L116
L165



2566.
L109
L117
L165



2567.
L109
L118
L165



2568.
L109
L119
L165



2569.
L109
L130
L165



2570.
L109
L131
L165



2571.
L109
L132
L165



2572.
L109
L133
L165



2573.
L109
L134
L165



2574.
L109
L140
L165



2575.
L109
L141
L165



2576.
L109
L159
L165



2577.
L109
L160
L165



2578.
L109
L110
L166



2579.
L109
L111
L166



2580.
L109
L112
L166



2581.
L109
L113
L166



2582.
L109
L114
L166



2583.
L109
L115
L166



2584.
L109
L116
L166



2585.
L109
L117
L166



2586.
L109
L118
L166



2587.
L109
L119
L166



2588.
L109
L130
L166



2589.
L109
L131
L166



2590.
L109
L132
L166



2591.
L109
L133
L166



2592.
L109
L134
L166



2593.
L109
L140
L166



2594.
L109
L141
L166



2595.
L109
L159
L166



2596.
L109
L160
L166



2597.
L109
L110
L170



2598.
L109
L111
L170



2599.
L109
L112
L170



2600.
L109
L113
L170



2601.
L109
L114
L170



2602.
L109
L115
L170



2603.
L109
L116
L170



2604.
L109
L117
L170



2605.
L109
L118
L170



2606.
L109
L119
L170



2607.
L109
L130
L170



2608.
L109
L131
L170



2609.
L109
L132
L170



2610.
L109
L133
L170



2611.
L109
L134
L170



2612.
L109
L140
L170



2613.
L109
L141
L170



2614.
L109
L159
L170



2615.
L109
L160
L170



2616.
L109
L110
L174



2617.
L109
L111
L174



2618.
L109
L112
L174



2619.
L109
L113
L174



2620.
L109
L114
L174



2621.
L109
L115
L174



2622.
L109
L116
L174



2623.
L109
L117
L174



2624.
L109
L118
L174



2625.
L109
L119
L174



2626.
L109
L130
L174



2627.
L109
L131
L174



2628.
L109
L132
L174



2629.
L109
L133
L174



2630.
L109
L134
L174



2631.
L109
L140
L174



2632.
L109
L141
L174



2633.
L109
L159
L174



2634.
L109
L160
L174



2635.
L109
L110
L176



2636.
L109
L111
L176



2637.
L109
L112
L176



2638.
L109
L113
L176



2639.
L109
L114
L176



2640.
L109
L115
L176



2641.
L109
L116
L176



2642.
L109
L117
L176



2643.
L109
L118
L176



2644.
L109
L119
L176



2645.
L109
L130
L176



2646.
L109
L131
L176



2647.
L109
L132
L176



2648.
L109
L133
L176



2649.
L109
L134
L176



2650.
L109
L140
L176



2651.
L109
L141
L176



2652.
L109
L159
L176



2653.
L109
L160
L176



2654.
L109
L110
L179



2655.
L109
L111
L179



2656.
L109
L112
L179



2657.
L109
L113
L179



2658.
L109
L114
L179



2659.
L109
L115
L179



2660.
L109
L116
L179



2661.
L109
L117
L179



2662.
L109
L118
L179



2663.
L109
L119
L179



2664.
L109
L130
L179



2665.
L109
L131
L179



2666.
L109
L132
L179



2667.
L109
L133
L179



2668.
L109
L134
L179



2669.
L109
L140
L179



2670.
L109
L141
L179



2671.
L109
L159
L179



2672.
L109
L160
L179



2673.
L109
L110
L180



2674.
L109
L111
L180



2675.
L109
L112
L180



2676.
L109
L113
L180



2677.
L109
L114
L180



2678.
L109
L115
L180



2679.
L109
L116
L180



2680.
L109
L117
L180



2681.
L109
L118
L180



2682.
L109
L119
L180



2683.
L109
L130
L180



2684.
L109
L131
L180



2685.
L109
L132
L180



2686.
L109
L133
L180



2687.
L109
L134
L180



2688.
L109
L140
L180



2689.
L109
L141
L180



2690.
L109
L159
L180



2691.
L109
L160
L180



2692.
L110
L111
L144



2693.
L110
L112
L144



2694.
L110
L113
L144



2695.
L110
L114
L144



2696.
L110
L115
L144



2697.
L110
L116
L144



2698.
L110
L117
L144



2699.
L110
L118
L144



2700.
L110
L119
L144



2701.
L110
L130
L144



2702.
L110
L131
L144



2703.
L110
L132
L144



2704.
L110
L133
L144



2705.
L110
L134
L144



2706.
L110
L140
L144



2707.
L110
L141
L144



2708.
L110
L159
L144



2709.
L110
L160
L144



2710.
L110
L110
L145



2711.
L110
L112
L145



2712.
L110
L113
L145



2713.
L110
L114
L145



2714.
L110
L115
L145



2715.
L110
L116
L145



2716.
L110
L117
L145



2717.
L110
L118
L145



2718.
L110
L119
L145



2719.
L110
L130
L145



2720.
L110
L131
L145



2721.
L110
L132
L145



2722.
L110
L133
L145



2723.
L110
L134
L145



2724.
L110
L140
L145



2725.
L110
L141
L145



2726.
L110
L159
L145



2727.
L110
L160
L145



2728.
L110
L111
L147



2729.
L110
L112
L147



2730.
L110
L113
L147



2731.
L110
L114
L147



2732.
L110
L115
L147



2733.
L110
L116
L147



2734.
L110
L117
L147



2735.
L110
L118
L147



2736.
L110
L119
L147



2737.
L110
L130
L147



2738.
L110
L131
L147



2739.
L110
L132
L147



2740.
L110
L133
L147



2741.
L110
L134
L147



2742.
L110
L140
L147



2743.
L110
L141
L147



2744.
L110
L159
L147



2745.
L110
L160
L147



2746.
L110
L111
L149



2747.
L110
L112
L149



2748.
L110
L113
L149



2749.
L110
L114
L149



2750.
L110
L115
L149



2751.
L110
L116
L149



2752.
L110
L117
L149



2753.
L110
L118
L149



2754.
L110
L119
L149



2755.
L110
L130
L149



2756.
L110
L131
L149



2757.
L110
L132
L149



2758.
L110
L133
L149



2759.
L110
L134
L149



2760.
L110
L140
L149



2761.
L110
L141
L149



2762.
L110
L159
L149



2763.
L110
L160
L149



2764.
L110
L111
L152



2765.
L110
L112
L152



2766.
L110
L113
L152



2767.
L110
L114
L152



2768.
L110
L115
L152



2769.
L110
L116
L152



2770.
L110
L117
L152



2771.
L110
L118
L152



2772.
L110
L119
L152



2773.
L110
L130
L152



2774.
L110
L131
L152



2775.
L110
L132
L152



2776.
L110
L133
L152



2777.
L110
L134
L152



2778.
L110
L140
L152



2779.
L110
L141
L152



2780.
L110
L159
L152



2781.
L110
L160
L152



2782.
L110
L111
L164



2783.
L110
L112
L164



2784.
L110
L113
L164



2785.
L110
L114
L164



2786.
L110
L115
L164



2787.
L110
L116
L164



2788.
L110
L117
L164



2789.
L110
L118
L164



2790.
L110
L119
L164



2791.
L110
L130
L164



2792.
L110
L131
L164



2793.
L110
L132
L164



2794.
L110
L133
L164



2795.
L110
L134
L164



2796.
L110
L140
L164



2797.
L110
L141
L164



2798.
L110
L159
L164



2799.
L110
L160
L164



2800.
L110
L111
L165



2801.
L110
L112
L165



2802.
L110
L113
L165



2803.
L110
L114
L165



2804.
L110
L115
L165



2805.
L110
L116
L165



2806.
L110
L117
L165



2807.
L110
L118
L165



2808.
L110
L119
L165



2809.
L110
L130
L165



2810.
L110
L131
L165



2811.
L110
L132
L165



2812.
L110
L133
L165



2813.
L110
L134
L165



2814.
L110
L140
L165



2815.
L110
L141
L165



2816.
L110
L159
L165



2817.
L110
L160
L165



2818.
L110
L111
L166



2819.
L110
L112
L166



2820.
L110
L113
L166



2821.
L110
L114
L166



2822.
L110
L115
L166



2823.
L110
L116
L166



2824.
L110
L117
L166



2825.
L110
L118
L166



2826.
L110
L119
L166



2827.
L110
L130
L166



2828.
L110
L131
L166



2829.
L110
L132
L166



2830.
L110
L133
L166



2831.
L110
L134
L166



2832.
L110
L140
L166



2833.
L110
L141
L166



2834.
L110
L159
L166



2835.
L110
L160
L166



2836.
L110
L111
L170



2837.
L110
L112
L170



2838.
L110
L113
L170



2839.
L110
L114
L170



2840.
L110
L115
L170



2841.
L110
L116
L170



2842.
L110
L117
L170



2843.
L110
L118
L170



2844.
L110
L119
L170



2845.
L110
L130
L170



2846.
L110
L131
L170



2847.
L110
L132
L170



2848.
L110
L133
L170



2849.
L110
L134
L170



2850.
L110
L140
L170



2851.
L110
L141
L170



2852.
L110
L159
L170



2853.
L110
L160
L170



2854.
L110
L111
L174



2855.
L110
L112
L174



2856.
L110
L113
L174



2857.
L110
L114
L174



2858.
L110
L115
L174



2859.
L110
L116
L174



2860.
L110
L117
L174



2861.
L110
L118
L174



2862.
L110
L119
L174



2863.
L110
L130
L174



2864.
L110
L131
L174



2865.
L110
L132
L174



2866.
L110
L133
L174



2867.
L110
L134
L174



2868.
L110
L140
L174



2869.
L110
L141
L174



2870.
L110
L159
L174



2871.
L110
L160
L174



2872.
L110
L111
L176



2873.
L110
L112
L176



2874.
L110
L113
L176



2875.
L110
L114
L176



2876.
L110
L115
L176



2877.
L110
L116
L176



2878.
L110
L117
L176



2879.
L110
L118
L176



2880.
L110
L119
L176



2881.
L110
L130
L176



2882.
L110
L131
L176



2883.
L110
L132
L176



2884.
L110
L133
L176



2885.
L110
L134
L176



2886.
L110
L140
L176



2887.
L110
L141
L176



2888.
L110
L159
L176



2889.
L110
L160
L176



2890.
L110
L111
L179



2891.
L110
L112
L179



2892.
L110
L113
L179



2893.
L110
L114
L179



2894.
L110
L115
L179



2895.
L110
L116
L179



2896.
L110
L117
L179



2897.
L110
L118
L179



2898.
L110
L119
L179



2899.
L110
L130
L179



2900.
L110
L131
L179



2901.
L110
L132
L179



2902.
L110
L133
L179



2903.
L110
L134
L179



2904.
L110
L140
L179



2905.
L110
L141
L179



2906.
L110
L159
L179



2907.
L110
L160
L179



2908.
L110
L111
L180



2909.
L110
L112
L180



2910.
L110
L113
L180



2911.
L110
L114
L180



2912.
L110
L115
L180



2913.
L110
L116
L180



2914.
L110
L117
L180



2915.
L110
L118
L180



2916.
L110
L119
L180



2917.
L110
L130
L180



2918.
L110
L131
L180



2919.
L110
L132
L180



2920.
L110
L133
L180



2921.
L110
L134
L180



2922.
L110
L135
L180



2923.
L110
L141
L180



2924.
L110
L159
L180



2925.
L110
L160
L180



2926.
L111
L112
L144



2927.
L111
L113
L144



2928.
L111
L114
L144



2929.
L111
L115
L144



2930.
L111
L116
L144



2931.
L111
L117
L144



2932.
L111
L118
L144



2933.
L111
L119
L144



2934.
L111
L130
L144



2935.
L111
L131
L144



2936.
L111
L132
L144



2937.
L111
L133
L144



2938.
L111
L134
L144



2939.
L111
L140
L144



2940.
L111
L141
L144



2941.
L111
L159
L144



2942.
L111
L160
L144



2943.
L111
L112
L145



2944.
L111
L113
L145



2945.
L111
L114
L145



2946.
L111
L115
L145



2947.
L111
L116
L145



2948.
L111
L117
L145



2949.
L111
L118
L145



2950.
L111
L119
L145



2951.
L111
L130
L145



2952.
L111
L131
L145



2953.
L111
L132
L145



2954.
L111
L133
L145



2955.
L111
L134
L145



2956.
L111
L140
L145



2957.
L111
L141
L145



2958.
L111
L159
L145



2959.
L111
L160
L145



2960.
L111
L112
L147



2961.
L111
L113
L147



2962.
L111
L114
L147



2963.
L111
L115
L147



2964.
L111
L116
L147



2695.
L111
L117
L147



2696.
L111
L118
L147



2697.
L111
L119
L147



2698.
L111
L130
L147



2699.
L111
L131
L147



2700.
L111
L132
L147



2701.
L111
L133
L147



2702.
L111
L134
L147



2703.
L111
L140
L147



2704.
L111
L141
L147



2705.
L111
L159
L147



2706.
L111
L160
L147



2707.
L111
L112
L149



2708.
L111
L113
L149



2709.
L111
L114
L149



2710.
L111
L115
L149



2711.
L111
L116
L149



2712.
L111
L117
L149



2713.
L111
L118
L149



2714.
L111
L119
L149



2715.
L111
L130
L149



2716.
L111
L131
L149



2717.
L111
L132
L149



2718.
L111
L133
L149



2719.
L111
L134
L149



2720.
L111
L140
L149



2721.
L111
L141
L149



2722.
L111
L159
L149



2723.
L111
L160
L149



2724.
L111
L112
L152



2725.
L111
L113
L152



2726.
L111
L114
L152



2727.
L111
L115
L152



2728.
L111
L116
L152



2729.
L111
L117
L152



2730.
L111
L118
L152



2731.
L111
L119
L152



2732.
L111
L130
L152



2733.
L111
L131
L152



2734.
L111
L132
L152



2735.
L111
L133
L152



2736.
L111
L134
L152



2737.
L111
L140
L152



2738.
L111
L141
L152



2739.
L111
L159
L152



2740.
L111
L160
L152



2741.
L111
L112
L164



2742.
L111
L113
L164



2743.
L111
L114
L164



2744.
L111
L115
L164



2745.
L111
L116
L164



2746.
L111
L117
L164



2747.
L111
L118
L164



2748.
L111
L119
L164



2749.
L111
L130
L164



2750.
L111
L131
L164



2751.
L111
L132
L164



2752.
L111
L133
L164



2753.
L111
L134
L164



2754.
L111
L140
L164



2755.
L111
L141
L164



2756.
L111
L159
L164



2757.
L111
L160
L164



2758.
L111
L112
L165



2759.
L111
L113
L165



2760.
L111
L114
L165



2761.
L111
L115
L165



2762.
L111
L116
L165



2763.
L111
L117
L165



2764.
L111
L118
L165



2765.
L111
L119
L165



2766.
L111
L130
L165



2767.
L111
L131
L165



2768.
L111
L132
L165



2769.
L111
L133
L165



2770.
L111
L134
L165



2771.
L111
L140
L165



2772.
L111
L141
L165



2773.
L111
L159
L165



2774.
L111
L160
L165



2775.
L111
L112
L166



2776.
L111
L113
L166



2777.
L111
L114
L166



2778.
L111
L115
L166



2779.
L111
L116
L166



2780.
L111
L117
L166



2781.
L111
L118
L166



2782.
L111
L119
L166



2783.
L111
L130
L166



2784.
L111
L131
L166



2785.
L111
L132
L166



2786.
L111
L133
L166



2787.
L111
L134
L166



2788.
L111
L140
L166



2789.
L111
L141
L166



2790.
L111
L159
L166



2791.
L111
L160
L166



2792.
L111
L112
L170



2793.
L111
L113
L170



2794.
L111
L114
L170



2795.
L111
L115
L170



2796.
L111
L116
L170



2797.
L111
L117
L170



2798.
L111
L118
L170



2799.
L111
L119
L170



2800.
L111
L130
L170



2801.
L111
L131
L170



2802.
L111
L132
L170



2803.
L111
L133
L170



2804.
L111
L134
L170



2805.
L111
L140
L170



2806.
L111
L141
L170



2807.
L111
L170
L170



2808.
L111
L160
L170



2809.
L111
L112
L174



2810.
L111
L113
L174



2811.
L111
L114
L174



2812.
L111
L115
L174



2813.
L111
L116
L174



2814.
L111
L117
L174



2815.
L111
L118
L174



2816.
L111
L119
L174



2817.
L111
L130
L174



2818.
L111
L131
L174



2819.
L111
L132
L174



2820.
L111
L133
L174



2821.
L111
L134
L174



2822.
L111
L140
L174



2823.
L111
L141
L174



2824.
L111
L159
L174



2825.
L111
L160
L174



2826.
L111
L112
L176



2827.
L111
L113
L176



2828.
L111
L114
L176



2829.
L111
L115
L176



2830.
L111
L116
L176



2831.
L111
L117
L176



2832.
L111
L118
L176



2833.
L111
L119
L176



2834.
L111
L130
L176



2835.
L111
L131
L176



2836.
L111
L132
L176



2837.
L111
L133
L176



2838.
L111
L134
L176



2839.
L111
L140
L176



2840.
L111
L141
L176



2841.
L111
L159
L176



2842.
L111
L160
L176



2843.
L111
L112
L179



2844.
L111
L113
L179



2845.
L111
L114
L179



2846.
L111
L115
L179



2847.
L111
L116
L179



2848.
L111
L117
L179



2849.
L111
L118
L179



2850.
L111
L119
L179



2851.
L111
L130
L179



2852.
L111
L131
L179



2853.
L111
L132
L179



2854.
L111
L133
L179



2855.
L111
L134
L179



2856.
L111
L140
L179



2857.
L111
L141
L179



2858.
L111
L159
L179



2859.
L111
L160
L179



2860.
L111
L112
L179



2861.
L111
L113
L180



2862.
L111
L114
L180



2863.
L111
L115
L180



2864.
L111
L116
L180



2865.
L111
L117
L180



2866.
L111
L118
L180



2867.
L111
L119
L180



2868.
L111
L130
L180



2869.
L111
L131
L180



2870.
L111
L132
L180



2871.
L111
L133
L180



2872.
L111
L134
L180



2873.
L111
L140
L180



2874.
L111
L141
L180



2875.
L111
L159
L180



2876.
L111
L160
L180



2877.
L112
L113
L144



2878.
L112
L114
L144



2879.
L112
L115
L144



2880.
L112
L116
L144



2881.
L112
L117
L144



2882.
L112
L118
L144



2883.
L112
L119
L144



2884.
L112
L130
L144



2885.
L112
L131
L144



2886.
L112
L132
L144



2887.
L112
L133
L144



2888.
L112
L134
L144



2889.
L112
L140
L144



2890.
L112
L141
L144



2891.
L112
L159
L144



2892.
L112
L160
L144



2893.
L112
L113
L145



2894.
L112
L114
L145



2895.
L112
L115
L145



2896.
L112
L116
L145



2897.
L112
L117
L145



2898.
L112
L118
L145



2899.
L112
L119
L145



2900.
L112
L130
L145



2901.
L112
L131
L145



2902.
L112
L132
L145



2903.
L112
L133
L145



2904.
L112
L134
L145



2905.
L112
L140
L145



2906.
L112
L141
L145



2907.
L112
L159
L145



2908.
L112
L160
L145



2909.
L112
L113
L147



2910.
L112
L114
L147



2911.
L112
L115
L147



2912.
L112
L116
L147



2913.
L112
L117
L147



2914.
L112
L118
L147



2915.
L112
L119
L147



2916.
L112
L130
L147



2917.
L112
L131
L147



2918.
L112
L132
L147



2919.
L112
L133
L147



2920.
L112
L134
L147



2921.
L112
L140
L147



2922.
L112
L141
L147



2923.
L112
L159
L147



2924.
L112
L160
L147



2925.
L112
L113
L149



2926.
L112
L114
L149



2927.
L112
L115
L149



2928.
L112
L116
L149



2929.
L112
L117
L149



2930.
L112
L118
L149



2931.
L112
L119
L149



2932.
L112
L130
L149



2933.
L112
L131
L149



2934.
L112
L132
L149



2935.
L112
L133
L149



2936.
L112
L134
L149



2937.
L112
L140
L149



2938.
L112
L141
L149



2939.
L112
L159
L149



2940.
L112
L160
L149



2941.
L112
L113
L152



2942.
L112
L114
L152



2943.
L112
L115
L152



2944.
L112
L116
L152



2945.
L112
L117
L152



2946.
L112
L118
L152



2947.
L112
L119
L152



2948.
L112
L130
L152



2949.
L112
L131
L152



2950.
L112
L132
L152



2951.
L112
L133
L152



2952.
L112
L134
L152



2953.
L112
L140
L152



2954.
L112
L141
L152



2955.
L112
L159
L152



2956.
L112
L160
L152



2957.
L112
L113
L164



2958.
L112
L114
L164



2959.
L112
L115
L164



2960.
L112
L116
L164



2961.
L112
L117
L164



2962.
L112
L118
L164



2963.
L112
L119
L164



2964.
L112
L130
L164



2965.
L112
L131
L164



2966.
L112
L132
L164



2967.
L112
L133
L164



2968.
L112
L134
L164



2969.
L112
L140
L164



2970.
L112
L141
L164



2971.
L112
L159
L164



2972.
L112
L160
L164



2973.
L112
L113
L165



2974.
L112
L114
L165



2975.
L112
L115
L165



2976.
L112
L116
L165



2977.
L112
L117
L165



2978.
L112
L118
L165



2979.
L112
L119
L165



2980.
L112
L130
L165



2981.
L112
L131
L165



2982.
L112
L132
L165



2983.
L112
L133
L165



2984.
L112
L134
L165



2985.
L112
L140
L165



2986.
L112
L141
L165



2987.
L112
L159
L165



2988.
L112
L160
L165



2989.
L112
L113
L166



2990.
L112
L114
L166



2991.
L112
L115
L166



2992.
L112
L116
L166



2993.
L112
L117
L166



2994.
L112
L118
L166



2995.
L112
L119
L166



2996.
L112
L130
L166



2997.
L112
L131
L166



2998.
L112
L132
L166



2999.
L112
L133
L166



3000.
L112
L134
L166



3001.
L112
L140
L166



3002.
L112
L141
L166



3003.
L112
L159
L166



3004.
L112
L160
L166



3005.
L112
L113
L170



3006.
L112
L114
L170



3007.
L112
L115
L170



3008.
L112
L116
L170



3009.
L112
L117
L170



3010.
L112
L118
L170



3011.
L112
L119
L170



3012.
L112
L130
L170



3013.
L112
L131
L170



3014.
L112
L132
L170



3015.
L112
L133
L170



3016.
L112
L134
L170



3017.
L112
L140
L170



3018.
L112
L141
L170



3019.
L112
L159
L170



3020.
L112
L160
L170



3021.
L112
L113
L174



3022.
L112
L114
L174



3023.
L112
L115
L174



3024.
L112
L116
L174



3025.
L112
L117
L174



3026.
L112
L118
L174



3027.
L112
L119
L174



3028.
L112
L130
L174



3029.
L112
L131
L174



3030.
L112
L132
L174



3031.
L112
L133
L174



3032.
L112
L134
L174



3033.
L112
L140
L174



3034.
L112
L141
L174



3035.
L112
L159
L174



3036.
L112
L160
L174



3037.
L112
L113
L176



3038.
L112
L114
L176



3039.
L112
L115
L176



3040.
L112
L116
L176



3041.
L112
L117
L176



3042.
L112
L118
L176



3043.
L112
L119
L176



3044.
L112
L130
L176



3045.
L112
L131
L176



3046.
L112
L132
L176



3047.
L112
L133
L176



3048.
L112
L134
L176



3049.
L112
L140
L176



3050.
L112
L141
L176



3051.
L112
L159
L176



3052.
L112
L160
L176



3053.
L112
L113
L179



3054.
L112
L114
L179



3055.
L112
L115
L179



3056.
L112
L116
L179



3057.
L112
L117
L179



3058.
L112
L118
L179



3059.
L112
L119
L179



3060.
L112
L130
L179



3061.
L112
L131
L179



3062.
L112
L132
L179



3063.
L112
L133
L179



3064.
L112
L134
L179



3065.
L112
L140
L179



3066.
L112
L141
L179



3067.
L112
L159
L179



3068.
L112
L160
L179



3069.
L112
L113
L180



3070.
L112
L114
L180



3071.
L112
L115
L180



3072.
L112
L116
L180



3073.
L112
L117
L180



3074.
L112
L118
L180



3075.
L112
L119
L180



3076.
L112
L130
L180



3077.
L112
L131
L180



3078.
L112
L132
L180



3079.
L112
L133
L180



3080.
L112
L134
L180



3081.
L112
L140
L180



3082.
L112
L141
L180



3083.
L112
L159
L180



3084.
L112
L160
L180



3085.
L113
L114
L144



3086.
L113
L115
L144



3087.
L113
L116
L144



3088.
L113
L117
L144



3089.
L113
L118
L144



3090.
L113
L119
L144



3091.
L113
L130
L144



3092.
L113
L131
L144



3093.
L113
L132
L144



3094.
L113
L133
L144



3095.
L113
L134
L144



3096.
L113
L140
L144



3097.
L113
L141
L144



3098.
L113
L159
L144



3099.
L113
L160
L144



3100.
L113
L114
L145



3101.
L113
L115
L145



3102.
L113
L116
L145



3103.
L113
L117
L145



3104.
L113
L118
L145



3105.
L113
L119
L145



3106.
L113
L130
L145



3107.
L113
L131
L145



3108.
L113
L132
L145



3109.
L113
L133
L145



3110.
L113
L134
L145



3111.
L113
L140
L145



3112.
L113
L141
L145



3113.
L113
L159
L145



3114.
L113
L160
L145



3115.
L113
L114
L147



3116.
L113
L115
L147



3117.
L113
L116
L147



3118.
L113
L117
L147



3119.
L113
L118
L147



3120.
L113
L119
L147



3121.
L113
L130
L147



3122.
L113
L131
L147



3123.
L113
L132
L147



3124.
L113
L133
L147



3125.
L113
L134
L147



3126.
L113
L140
L147



3127.
L113
L141
L147



3128.
L113
L159
L147



3129.
L113
L160
L147



3130.
L113
L114
L149



3131.
L113
L115
L149



3132.
L113
L116
L149



3133.
L113
L117
L149



3134.
L113
L118
L149



3135.
L113
L119
L149



3136.
L113
L130
L149



3137.
L113
L131
L149



3138.
L113
L132
L149



3139.
L113
L133
L149



3140.
L113
L134
L149



3141.
L113
L140
L149



3142.
L113
L141
L149



3143.
L113
L159
L149



3144.
L113
L160
L149



3145.
L113
L114
L152



3146.
L113
L115
L152



3147.
L113
L116
L152



3148.
L113
L117
L152



3149.
L113
L118
L152



3150.
L113
L119
L152



3151.
L113
L130
L152



3152.
L113
L131
L152



3153.
L113
L132
L152



3154.
L113
L133
L152



3155.
L113
L134
L152



3156.
L113
L140
L152



3157.
L113
L141
L152



3158.
L113
L159
L152



3159.
L113
L160
L152



3160.
L113
L114
L164



3161.
L113
L115
L164



3162.
L113
L116
L164



3163.
L113
L117
L164



3164.
L113
L118
L164



3165.
L113
L119
L164



3166.
L113
L130
L164



3167.
L113
L131
L164



3168.
L113
L132
L164



3169.
L113
L133
L164



3170.
L113
L134
L164



3171.
L113
L140
L164



3172.
L113
L141
L164



3173.
L113
L159
L164



3174.
L113
L160
L164



3175.
L113
L114
L165



3176.
L113
L115
L165



3177.
L113
L116
L165



3178.
L113
L117
L165



3179.
L113
L118
L165



3180.
L113
L119
L165



3181.
L113
L130
L165



3182.
L113
L131
L165



3183.
L113
L132
L165



3184.
L113
L133
L165



3185.
L113
L134
L165



3186.
L113
L140
L165



3187.
L113
L141
L165



3188.
L113
L159
L165



3189.
L113
L160
L165



3190.
L113
L114
L166



3191.
L113
L115
L166



3192.
L113
L116
L166



3193.
L113
L117
L166



3194.
L113
L118
L166



3195.
L113
L119
L166



3196.
L113
L130
L166



3197.
L113
L131
L166



3198.
L113
L132
L166



3199.
L113
L133
L166



3200.
L113
L134
L166



3201.
L113
L140
L166



3202.
L113
L141
L166



3203.
L113
L159
L166



3204.
L113
L160
L166



3205.
L113
L114
L170



3206.
L113
L115
L170



3207.
L113
L116
L170



3208.
L113
L117
L170



3209.
L113
L118
L170



3210.
L113
L119
L170



3211.
L113
L130
L170



3212.
L113
L131
L170



3213.
L113
L132
L170



3214.
L113
L133
L170



3215.
L113
L134
L170



3216.
L113
L140
L170



3217.
L113
L141
L170



3218.
L113
L159
L170



3219.
L113
L160
L170



3220.
L113
L114
L174



3221.
L113
L115
L174



3222.
L113
L116
L174



3223.
L113
L117
L174



3224.
L113
L118
L174



3225.
L113
L119
L174



3226.
L113
L130
L174



3227.
L113
L131
L174



3228.
L113
L132
L174



3229.
L113
L133
L174



3230.
L113
L134
L174



3231.
L113
L140
L174



3232.
L113
L141
L174



3233.
L113
L159
L174



3234.
L113
L160
L174



3235.
L113
L114
L176



3236.
L113
L115
L176



3237.
L113
L116
L176



3238.
L113
L117
L176



3239.
L113
L118
L176



3240.
L113
L119
L176



3241.
L113
L130
L176



3242.
L113
L131
L176



3243.
L113
L132
L176



3244.
L113
L133
L176



3245.
L113
L134
L176



3246.
L113
L140
L176



3247.
L113
L141
L176



3248.
L113
L159
L176



3249.
L113
L160
L176



3250.
L113
L114
L179



3251.
L113
L115
L179



3252.
L113
L116
L179



3253.
L113
L117
L179



3254.
L113
L118
L179



3255.
L113
L119
L179



3256.
L113
L130
L179



3257.
L113
L131
L179



3258.
L113
L132
L179



3259.
L113
L133
L179



3260.
L113
L134
L179



3261.
L113
L140
L179



3262.
L113
L141
L179



3263.
L113
L159
L179



3264.
L113
L160
L179



3265.
L113
L114
L180



3266.
L113
L115
L180



3267.
L113
L116
L180



3268.
L113
L117
L180



3269.
L113
L118
L180



3270.
L113
L119
L180



3271.
L113
L130
L180



3272.
L113
L131
L180



3273.
L113
L132
L180



3274.
L113
L133
L180



3275.
L113
L134
L180



3276.
L113
L140
L180



3277.
L113
L141
L180



3278.
L113
L159
L180



3279.
L113
L160
L180



3280.
L114
L115
L144



3281.
L114
L116
L144



3282.
L114
L117
L144



3283.
L114
L118
L144



3284.
L114
L119
L144



3285.
L114
L130
L144



3286.
L114
L131
L144



3287.
L114
L132
L144



3288.
L114
L133
L144



3289.
L114
L134
L144



3290.
L114
L140
L144



3291.
L114
L141
L144



3292.
L114
L159
L144



3293.
L114
L160
L144



3294.
L114
L115
L145



3295.
L114
L116
L145



3296.
L114
L117
L145



3297.
L114
L118
L145



3298.
L114
L119
L145



3299.
L114
L130
L145



3300.
L114
L131
L145



3301.
L114
L132
L145



3302.
L114
L133
L145



3303.
L114
L134
L145



3304.
L114
L140
L145



3305.
L114
L141
L145



3306.
L114
L159
L145



3307.
L114
L160
L145



3308.
L114
L115
L147



3309.
L114
L116
L147



3310.
L114
L117
L147



3311.
L114
L118
L147



3312.
L114
L119
L147



3313.
L114
L130
L147



3314.
L114
L131
L147



3315.
L114
L132
L147



3316.
L114
L133
L147



3317.
L114
L134
L147



3318.
L114
L140
L147



3319.
L114
L141
L147



3320.
L114
L159
L147



3321.
L114
L160
L147



3322.
L114
L115
L149



3323.
L114
L116
L149



3324.
L114
L117
L149



3325.
L114
L118
L149



3326.
L114
L119
L149



3327.
L114
L130
L149



3328.
L114
L131
L149



3329.
L114
L132
L149



3330.
L114
L133
L149



3331.
L114
L134
L149



3332.
L114
L140
L149



3333.
L114
L141
L149



3334.
L114
L159
L149



3335.
L114
L160
L149



3336.
L114
L115
L152



3337.
L114
L116
L152



3338.
L114
L117
L152



3339.
L114
L118
L152



3340.
L114
L119
L152



3341.
L114
L130
L152



3342.
L114
L131
L152



3343.
L114
L132
L152



3344.
L114
L133
L152



3345.
L114
L134
L152



3346.
L114
L140
L152



3347.
L114
L141
L152



3348.
L114
L159
L152



3349.
L114
L160
L152



3350.
L114
L115
L164



3351.
L114
L116
L164



3352.
L114
L117
L164



3353.
L114
L118
L164



3354.
L114
L119
L164



3355.
L114
L130
L164



3356.
L114
L131
L164



3357.
L114
L132
L164



3358.
L114
L133
L164



3359.
L114
L134
L164



3360.
L114
L140
L164



3361.
L114
L141
L164



3362.
L114
L159
L164



3363.
L114
L160
L164



3364.
L114
L115
L165



3365.
L114
L116
L165



3366.
L114
L117
L165



3367.
L114
L118
L165



3368.
L114
L119
L165



3369.
L114
L130
L165



3370.
L114
L131
L165



3371.
L114
L132
L165



3372.
L114
L133
L165



3373.
L114
L134
L165



3374.
L114
L140
L165



3375.
L114
L141
L165



3376.
L114
L159
L165



3377.
L114
L160
L165



3378.
L114
L115
L166



3379.
L114
L116
L166



3380.
L114
L117
L166



3381.
L114
L118
L166



3382.
L114
L119
L166



3383.
L114
L130
L166



3384.
L114
L131
L166



3385.
L114
L132
L166



3386.
L114
L133
L166



3387.
L114
L134
L166



3388.
L114
L140
L166



3389.
L114
L141
L166



3390.
L114
L159
L166



3391.
L114
L160
L166



3392.
L114
L115
L170



3393.
L114
L116
L170



3394.
L114
L117
L170



3395.
L114
L118
L170



3396.
L114
L119
L170



3397.
L114
L130
L170



3398.
L114
L131
L170



3399.
L114
L132
L170



3400.
L114
L133
L170



3401.
L114
L134
L170



3402.
L114
L140
L170



3403.
L114
L141
L170



3404.
L114
L159
L170



3405.
L114
L160
L170



3406.
L114
L115
L174



3407.
L114
L116
L174



3408.
L114
L117
L174



3409.
L114
L118
L174



3410.
L114
L119
L174



3411.
L114
L130
L174



3412.
L114
L131
L174



3413.
L114
L132
L174



3414.
L114
L133
L174



3415.
L114
L134
L174



3416.
L114
L140
L174



3417.
L114
L141
L174



3418.
L114
L159
L174



3419.
L114
L160
L174



3420.
L114
L115
L176



3421.
L114
L116
L176



3422.
L114
L117
L176



3423.
L114
L118
L176



3424.
L114
L119
L176



3425.
L114
L130
L176



3426.
L114
L131
L176



3427.
L114
L132
L176



3428.
L114
L133
L176



3429.
L114
L134
L176



3430.
L114
L140
L176



3431.
L114
L141
L176



3432.
L114
L159
L176



3433.
L114
L160
L176



3434.
L114
L115
L179



3435.
L114
L116
L179



3436.
L114
L117
L179



3437.
L114
L118
L179



3438.
L114
L119
L179



3439.
L114
L130
L179



3440.
L114
L131
L179



3441.
L114
L132
L179



3442.
L114
L133
L179



3443.
L114
L134
L179



3444.
L114
L140
L179



3445.
L114
L141
L179



3446.
L114
L159
L179



3447.
L114
L160
L179



3448.
L114
L115
L180



3449.
L114
L116
L180



3450.
L114
L117
L180



3451.
L114
L118
L180



3452.
L114
L119
L180



3453.
L114
L130
L180



3454.
L114
L131
L180



3455.
L114
L132
L180



3456.
L114
L133
L180



3457.
L114
L134
L180



3458.
L114
L140
L180



3459.
L114
L141
L180



3460.
L114
L159
L180



3461.
L114
L160
L180



3462.
L115
L116
L144



3463.
L115
L117
L144



3464.
L115
L118
L144



3465.
L115
L119
L144



3466.
L115
L130
L144



3467.
L115
L131
L144



3468.
L115
L132
L144



3469.
L115
L133
L144



3470.
L115
L134
L144



3471.
L115
L140
L144



3472.
L115
L141
L144



3473.
L115
L159
L144



3474.
L115
L160
L144



3475.
L115
L116
L145



3476.
L115
L117
L145



3477.
L115
L118
L145



3478.
L115
L119
L145



3479.
L115
L130
L145



3480.
L115
L131
L145



3481.
L115
L132
L145



3482.
L115
L133
L145



3483.
L115
L134
L145



3484.
L115
L140
L145



3485.
L115
L141
L145



3486.
L115
L159
L145



3487.
L115
L160
L145



3488.
L115
L116
L147



3489.
L115
L117
L147



3490.
L115
L118
L147



3491.
L115
L119
L147



3492.
L115
L130
L147



3493.
L115
L131
L147



3494.
L115
L132
L147



3495.
L115
L133
L147



3496.
L115
L134
L147



3497.
L115
L140
L147



3498.
L115
L141
L147



3499.
L115
L159
L147



3500.
L115
L160
L147



3501.
L115
L116
L149



3502.
L115
L117
L149



3503.
L115
L118
L149



3504.
L115
L119
L149



3505.
L115
L130
L149



3506.
L115
L131
L149



3507.
L115
L132
L149



3508.
L115
L133
L149



3509.
L115
L134
L149



3510.
L115
L140
L149



3511.
L115
L141
L149



3512.
L115
L159
L149



3513.
L115
L160
L149



3514.
L115
L116
L152



3515.
L115
L117
L152



3516.
L115
L118
L152



3517.
L115
L119
L152



3518.
L115
L130
L152



3519.
L115
L131
L152



3520.
L115
L132
L152



3521.
L115
L133
L152



3522.
L115
L134
L152



3523.
L115
L140
L152



3524.
L115
L141
L152



3525.
L115
L159
L152



3526.
L115
L160
L152



3527.
L115
L116
L164



3528.
L115
L117
L164



3529.
L115
L118
L164



3530.
L115
L119
L164



3531.
L115
L130
L164



3532.
L115
L131
L164



3533.
L115
L132
L164



3534.
L115
L133
L164



3535.
L115
L134
L164



3536.
L115
L140
L164



3537.
L115
L141
L164



3538.
L115
L159
L164



3539.
L115
L160
L164



3540.
L115
L116
L165



3541.
L115
L117
L165



3542.
L115
L118
L165



3543.
L115
L119
L165



3544.
L115
L130
L165



3545.
L115
L131
L165



3546.
L115
L132
L165



3547.
L115
L133
L165



3548.
L115
L134
L165



3549.
L115
L140
L165



3550.
L115
L141
L165



3551.
L115
L159
L165



3552.
L115
L160
L165



3553.
L115
L116
L166



3554.
L115
L117
L166



3555.
L115
L118
L166



3556.
L115
L119
L166



3557.
L115
L130
L166



3558.
L115
L131
L166



3559.
L115
L132
L166



3560.
L115
L133
L166



3561.
L115
L134
L166



3562.
L115
L140
L166



3563.
L115
L141
L166



3564.
L115
L159
L166



3565.
L115
L160
L166



3566.
L115
L116
L170



3567.
L115
L117
L170



3568.
L115
L118
L170



3569.
L115
L119
L170



3570.
L115
L130
L170



3571.
L115
L131
L170



3572.
L115
L132
L170



3573.
L115
L133
L170



3574.
L115
L134
L170



3575.
L115
L140
L170



3576.
L115
L141
L170



3577.
L115
L159
L170



3578.
L115
L160
L170



3579.
L115
L116
L174



3580.
L115
L117
L174



3581.
L115
L118
L174



3582.
L115
L119
L174



3583.
L115
L130
L174



3584.
L115
L131
L174



3585.
L115
L132
L174



3586.
L115
L133
L174



3587.
L115
L134
L174



3588.
L115
L140
L174



3589.
L115
L141
L174



3590.
L115
L159
L174



3591.
L115
L160
L174



3592.
L115
L116
L176



3593.
L115
L117
L176



3594.
L115
L118
L176



3595.
L115
L119
L176



3596.
L115
L130
L176



3597.
L115
L131
L176



3598.
L115
L132
L176



3599.
L115
L133
L176



3600.
L115
L134
L176



3601.
L115
L140
L176



3602.
L115
L141
L176



3603.
L115
L159
L176



3604.
L115
L160
L176



3605.
L115
L116
L179



3606.
L115
L117
L179



3607.
L115
L118
L179



3608.
L115
L119
L179



3609.
L115
L130
L179



3610.
L115
L131
L179



3611.
L115
L132
L179



3612.
L115
L133
L179



3613.
L115
L134
L179



3614.
L115
L140
L179



3615.
L115
L141
L179



3616.
L115
L159
L179



3617.
L115
L160
L179



3618.
L115
L116
L180



3619.
L115
L117
L180



3620.
L115
L118
L180



3621.
L115
L119
L180



3622.
L115
L130
L180



3623.
L115
L131
L180



3624.
L115
L132
L180



3625.
L115
L133
L180



3626.
L115
L134
L180



3627.
L115
L140
L180



3628.
L115
L141
L180



3629.
L115
L159
L180



3630.
L115
L160
L180



3631.
L116
L117
L144



3632.
L116
L118
L144



3633.
L116
L119
L144



3634.
L116
L130
L144



3635.
L115
L131
L144



3636.
L116
L132
L144



3637.
L116
L133
L144



3638.
L116
L134
L144



3639.
L116
L140
L144



3640.
L116
L141
L144



3641.
L116
L159
L144



3642.
L116
L160
L144



3643.
L116
L117
L145



3644.
L116
L118
L145



3645.
L116
L119
L145



3646.
L116
L130
L145



3647.
L116
L131
L145



3648.
L116
L132
L145



3649.
L116
L133
L145



3650.
L116
L134
L145



3651.
L116
L140
L145



3652.
L116
L141
L145



3653.
L116
L159
L145



3654.
L116
L160
L145



3655.
L116
L117
L147



3656.
L116
L118
L147



3657.
L116
L119
L147



3658.
L116
L130
L147



3659.
L116
L131
L147



3660.
L116
L132
L147



3661.
L116
L133
L147



3662.
L116
L134
L147



3663.
L116
L140
L147



3664.
L116
L141
L147



3665.
L116
L159
L147



3666.
L116
L160
L147



3667.
L116
L117
L149



3668.
L116
L118
L149



3669.
L116
L119
L149



3670.
L116
L130
L149



3671.
L116
L131
L149



3672.
L116
L132
L149



3673.
L116
L133
L149



3674.
L116
L134
L149



3675.
L116
L140
L149



3676.
L116
L141
L149



3677.
L116
L159
L149



3678.
L116
L160
L149



3679.
L116
L117
L152



3680.
L116
L118
L152



3681.
L116
L119
L152



3682.
L116
L130
L152



3683.
L116
L131
L152



3684.
L116
L132
L152



3685.
L116
L133
L152



3686.
L116
L134
L152



3687.
L116
L140
L152



3688.
L116
L141
L152



3689.
L116
L159
L152



3690.
L116
L160
L152



3691.
L116
L117
L164



3692.
L116
L118
L164



3693.
L116
L119
L164



3694.
L116
L130
L164



3695.
L116
L131
L164



3696.
L116
L132
L164



3697.
L116
L133
L164



3698.
L116
L134
L164



3699.
L116
L140
L164



3700.
L116
L141
L164



3701.
L116
L159
L164



3702.
L116
L160
L164



3703.
L116
L117
L165



3704.
L116
L118
L165



3705.
L116
L119
L164



3706.
L116
L130
L164



3707.
L116
L131
L165



3708.
L116
L132
L165



3709.
L116
L133
L165



3710.
L116
L134
L165



3711.
L116
L140
L165



3712.
L116
L141
L165



3713.
L116
L159
L165



3714.
L116
L160
L165



3715.
L116
L117
L166



3716.
L116
L118
L166



3717.
L116
L119
L166



3718.
L116
L130
L166



3719.
L116
L131
L166



3720.
L116
L132
L166



3721.
L116
L133
L166



3722.
L116
L134
L166



3723.
L116
L140
L166



3724.
L116
L141
L166



3725.
L116
L159
L166



3726.
L116
L160
L166



3727.
L116
L117
L170



3728.
L116
L118
L170



3729.
L116
L119
L170



3730.
L116
L130
L170



3731.
L116
L131
L170



3732.
L116
L132
L170



3733.
L116
L133
L170



3734.
L116
L134
L170



3735.
L116
L140
L170



3736.
L116
L141
L170



3737.
L116
L159
L170



3738.
L116
L160
L170



3739.
L116
L117
L174



3740.
L116
L118
L174



3741.
L116
L119
L174



3742.
L116
L130
L174



3743.
L116
L131
L174



3744.
L116
L132
L174



3745.
L116
L133
L174



3746.
L116
L134
L174



3747.
L116
L140
L174



3748.
L116
L141
L174



3749.
L116
L159
L174



3750.
L116
L160
L174



3751.
L116
L117
L176



3752.
L116
L118
L176



3753.
L116
L119
L176



3754.
L116
L130
L176



3755.
L116
L131
L176



3756.
L116
L132
L176



3757.
L116
L133
L176



3758.
L116
L134
L176



3759.
L116
L140
L176



3760.
L116
L141
L176



3761.
L116
L159
L176



3762.
L116
L160
L176



3763.
L116
L117
L179



3764.
L116
L118
L179



3765.
L116
L119
L179



3766.
L116
L130
L179



3767.
L116
L131
L179



3768.
L116
L132
L179



3769.
L116
L133
L179



3770.
L116
L134
L179



3771.
L116
L140
L179



3772.
L116
L141
L179



3773.
L116
L159
L179



3774.
L116
L160
L179



3775.
L116
L117
L180



3776.
L116
L118
L180



3777.
L116
L119
L180



3778.
L116
L130
L180



3779.
L116
L131
L180



3780.
L116
L132
L180



3781.
L116
L133
L180



3782.
L116
L134
L180



3783.
L116
L140
L180



3784.
L116
L141
L180



3785.
L116
L159
L180



3786.
L116
L160
L180



3787.
L116
L118
L144



3788.
L116
L119
L144



3789.
L116
L130
L144



3790.
L117
L131
L144



3791.
L117
L132
L144



3792.
L117
L133
L144



3793.
L117
L134
L144



3794.
L117
L140
L144



3795.
L117
L141
L144



3796.
L117
L159
L144



3797.
L117
L160
L144



3798.
L117
L118
L145



3799.
L117
L119
L145



3800.
L117
L130
L145



3801.
L117
L131
L145



3802.
L117
L132
L145



3803.
L117
L133
L145



3804.
L117
L134
L145



3805.
L117
L140
L145



3806.
L117
L141
L145



3807.
L117
L159
L145



3808.
L117
L160
L145



3809.
L117
L118
L147



3810.
L117
L119
L147



3811.
L117
L130
L147



3812.
L117
L131
L147



3813.
L117
L132
L147



3814.
L117
L133
L147



3815.
L117
L134
L147



3816.
L117
L140
L147



3817.
L117
L141
L147



3818.
L117
L159
L147



3819.
L117
L160
L147



3820.
L117
L118
L149



3821.
L117
L119
L149



3822.
L117
L130
L149



3823.
L117
L131
L149



3824.
L117
L132
L149



3825.
L117
L133
L149



3826.
L117
L134
L149



3827.
L117
L140
L149



3828.
L117
L141
L149



3829.
L117
L159
L149



3830.
L117
L160
L149



3831.
L117
L118
L152



3832.
L117
L119
L152



3833.
L117
L130
L152



3834.
L117
L131
L152



3835.
L117
L132
L152



3836.
L117
L133
L152



3837.
L117
L134
L152



3838.
L117
L140
L152



3839.
L117
L141
L152



3840.
L117
L159
L152



3841.
L117
L160
L152



3842.
L117
L118
L164



3843.
L117
L119
L164



3844.
L117
L130
L164



3845.
L117
L131
L164



3846.
L117
L132
L164



3847.
L117
L133
L164



3848.
L117
L134
L164



3849.
L117
L140
L164



3850.
L117
L141
L164



3851.
L117
L159
L164



3852.
L117
L160
L164



3853.
L117
L118
L165



3854.
L117
L119
L165



3855.
L117
L130
L165



3856.
L117
L131
L165



3857.
L117
L132
L165



3858.
L117
L133
L165



3859.
L117
L134
L165



3860.
L117
L140
L165



3861.
L117
L141
L165



3862.
L117
L159
L165



3863.
L117
L160
L165



3864.
L117
L118
L166



3865.
L117
L119
L166



3866.
L117
L130
L166



3867.
L117
L131
L166



3868.
L117
L132
L166



3869.
L117
L133
L166



3870.
L117
L134
L166



3871.
L117
L140
L166



3872.
L117
L141
L166



3873.
L117
L159
L166



3874.
L117
L160
L166



3875.
L117
L118
L170



3876.
L117
L119
L170



3877.
L117
L130
L170



3878.
L117
L131
L170



3879.
L117
L132
L170



3880.
L117
L133
L170



3881.
L117
L134
L170



3882.
L117
L140
L170



3883.
L117
L141
L170



3884.
L117
L159
L170



3885.
L117
L160
L170



3886.
L117
L118
L174



3887.
L117
L119
L174



3888.
L117
L130
L174



3889.
L117
L131
L174



3890.
L117
L132
L174



3891.
L117
L133
L174



3892.
L117
L134
L174



3893.
L117
L140
L174



3894.
L117
L141
L174



3895.
L117
L159
L174



3896.
L117
L160
L174



3897.
L117
L118
L176



3898.
L117
L119
L176



3899.
L117
L130
L176



3900.
L117
L131
L176



3901.
L117
L132
L176



3902.
L117
L133
L176



3903.
L117
L134
L176



3904.
L117
L140
L176



3905.
L117
L141
L176



3906.
L117
L159
L176



3907.
L117
L160
L176



3908.
L117
L118
L179



3909.
L117
L119
L179



3910.
L117
L130
L179



3911.
L117
L131
L179



3912.
L117
L132
L179



3913.
L117
L133
L179



3914.
L117
L134
L179



3915.
L117
L140
L179



3916.
L117
L141
L179



3917.
L117
L159
L179



3918.
L117
L160
L179



3919.
L117
L118
L180



3920.
L117
L119
L180



3921.
L117
L130
L180



3922.
L117
L131
L180



3923.
L117
L132
L180



3924.
L117
L133
L180



3925.
L117
L134
L180



3926.
L117
L140
L180



3927.
L117
L141
L180



3928.
L117
L159
L180



3929.
L117
L160
L180



3930.
L118
L119
L144



3931.
L118
L130
L144



3932.
L118
L131
L144



3933.
L118
L132
L144



3934.
L118
L133
L144



3935.
L118
L134
L144



3936.
L118
L140
L144



3937.
L118
L141
L144



3938.
L118
L159
L144



3939.
L118
L160
L144



3940.
L118
L119
L145



3941.
L118
L130
L145



3942.
L118
L131
L145



3943.
L118
L132
L145



3944.
L118
L133
L145



3945.
L118
L134
L145



3946.
L118
L140
L145



3947.
L118
L141
L145



3948.
L118
L159
L145



3949.
L118
L160
L145



3950.
L118
L119
L147



3951.
L118
L130
L147



3952.
L118
L131
L147



3953.
L118
L132
L147



3954.
L118
L133
L147



3955.
L118
L134
L147



3956.
L118
L140
L147



3957.
L118
L141
L147



3958.
L118
L159
L147



3959.
L118
L160
L147



3960.
L118
L119
L149



3961.
L118
L130
L149



3962.
L118
L131
L149



3963.
L118
L132
L149



3964.
L118
L133
L149



3965.
L118
L134
L149



3966.
L118
L140
L149



3967.
L118
L141
L149



3968.
L118
L159
L149



3969.
L118
L160
L149



3970.
L118
L119
L152



3971.
L118
L130
L152



3972.
L118
L131
L152



3973.
L118
L132
L152



3974.
L118
L133
L152



3975.
L118
L134
L152



3976.
L118
L140
L152



3977.
L118
L141
L152



3978.
L118
L159
L152



3979.
L118
L160
L152



3980.
L118
L119
L164



3981.
L118
L130
L164



3982.
L118
L131
L164



3983.
L118
L132
L164



3984.
L118
L133
L164



3985.
L118
L134
L164



3986.
L118
L140
L164



3987.
L118
L141
L164



3988.
L118
L159
L164



3989.
L118
L160
L164



3990.
L118
L119
L165



3991.
L118
L130
L165



3992.
L118
L131
L165



3993.
L118
L132
L165



3994.
L118
L133
L165



3995.
L118
L134
L165



3996.
L118
L140
L165



3997.
L118
L141
L165



3998.
L118
L159
L165



3999.
L118
L160
L165



4000.
L118
L119
L166



4001.
L118
L130
L166



4002.
L118
L131
L166



4003.
L118
L132
L166



4004.
L118
L133
L166



4005.
L118
L134
L166



4006.
L118
L140
L166



4007.
L118
L141
L166



4008.
L118
L159
L166



4009.
L118
L160
L166



4010.
L118
L119
L170



4011.
L118
L130
L170



4012.
L118
L131
L170



4013.
L118
L132
L170



4014.
L118
L133
L170



4015.
L118
L134
L170



4016.
L118
L140
L170



4017.
L118
L141
L170



4018.
L118
L159
L170



4019.
L118
L160
L170



4020.
L118
L119
L174



4021.
L118
L130
L174



4022.
L118
L131
L174



4023.
L118
L132
L174



4024.
L118
L133
L174



4025.
L118
L134
L174



4026.
L118
L140
L174



4027.
L118
L141
L174



4028.
L118
L159
L174



4029.
L118
L160
L174



4030.
L118
L119
L176



4031.
L118
L130
L176



4032.
L118
L131
L176



4033.
L118
L132
L176



4034.
L118
L133
L176



4035.
L118
L134
L176



4036.
L118
L140
L176



4037.
L118
L141
L176



4038.
L118
L159
L176



4039.
L118
L160
L176



4040.
L118
L119
L179



4041.
L118
L130
L179



4042.
L118
L131
L179



4043.
L118
L132
L179



4044.
L118
L133
L179



4045.
L118
L134
L179



4046.
L118
L140
L179



4047.
L118
L141
L179



4048.
L118
L159
L179



4049.
L118
L160
L179



4050.
L118
L119
L180



4051.
L118
L130
L180



4052.
L118
L131
L180



4053.
L118
L132
L180



4054.
L118
L133
L180



4055.
L118
L134
L180



4056.
L118
L140
L180



4057.
L118
L141
L180



4058.
L118
L159
L180



4059.
L118
L160
L180



4060.
L119
L130
L144



4061.
L119
L131
L144



4062.
L119
L132
L144



4063.
L119
L133
L144



4064.
L119
L134
L144



4065.
L119
L140
L144



4066.
L119
L141
L144



4067.
L119
L159
L144



4068.
L119
L160
L144



4069.
L119
L130
L145



4070.
L119
L131
L145



4071.
L119
L132
L145



4072.
L119
L133
L145



4073.
L119
L134
L145



4074.
L119
L140
L145



4075.
L119
L141
L145



4076.
L119
L159
L145



4077.
L119
L160
L145



4078.
L119
L130
L147



4079.
L119
L131
L147



4080.
L119
L132
L147



4081.
L119
L133
L147



4082.
L119
L134
L147



4083.
L119
L140
L147



4084.
L119
L141
L147



4085.
L119
L159
L147



4086.
L119
L160
L147



4087.
L119
L130
L149



4088.
L119
L131
L149



4089.
L119
L132
L149



4090.
L119
L133
L149



4091.
L119
L134
L149



4092.
L119
L140
L149



4093.
L119
L141
L149



4094.
L119
L159
L149



4095.
L119
L160
L149



4096.
L119
L130
L152



4097.
L119
L131
L152



4098.
L119
L132
L152



4099.
L119
L133
L152



4100.
L119
L134
L152



4101.
L119
L140
L152



4102.
L119
L141
L152



4103.
L119
L159
L152



4104.
L119
L160
L152



4105.
L119
L130
L164



4106.
L119
L131
L164



4107.
L119
L132
L164



4108.
L119
L133
L164



4109.
L119
L134
L164



4110.
L119
L140
L164



4111.
L119
L141
L164



4112.
L119
L159
L164



4113.
L119
L160
L164



4114.
L119
L130
L165



4115.
L119
L131
L165



4116.
L119
L132
L165



4117.
L119
L133
L165



4118.
L119
L134
L165



4119.
L119
L140
L165



4120.
L119
L141
L165



4121.
L119
L159
L165



4122.
L119
L160
L165



4123.
L119
L130
L166



4124.
L119
L131
L166



4125.
L119
L132
L166



4126.
L119
L133
L166



4127.
L119
L134
L166



4128.
L119
L140
L166



4129.
L119
L141
L166



4130.
L119
L159
L166



4131.
L119
L160
L166



4132.
L119
L130
L170



4133.
L119
L131
L170



4134.
L119
L132
L170



4135.
L119
L133
L170



4136.
L119
L134
L170



4137.
L119
L140
L170



4138.
L119
L141
L170



4139.
L119
L159
L170



4140.
L119
L160
L170



4141.
L119
L130
L174



4142.
L119
L131
L174



4143.
L119
L132
L174



4144.
L119
L133
L174



4145.
L119
L134
L174



4146.
L119
L140
L174



4147.
L119
L141
L174



4148.
L119
L159
L174



4149.
L119
L160
L174



4150.
L119
L130
L176



4151.
L119
L131
L176



4152.
L119
L132
L176



4153.
L119
L133
L176



4154.
L119
L134
L176



4155.
L119
L140
L176



4156.
L119
L141
L176



4157.
L119
L159
L176



4158.
L119
L160
L170



4159.
L119
L130
L179



4160.
L119
L131
L179



4161.
L119
L132
L179



4162.
L119
L133
L179



4163.
L119
L134
L179



4164.
L119
L140
L179



4165.
L119
L141
L179



4166.
L119
L159
L179



4167.
L119
L160
L179



4168.
L119
L130
L180



4169.
L119
L131
L180



4170.
L119
L132
L180



4171.
L119
L133
L180



4172.
L119
L134
L180



4173.
L119
L140
L180



4174.
L119
L141
L180



4175.
L119
L159
L180



4176.
L119
L160
L180










According to one embodiment, the following Table 2 lists a group of preferred compounds:


















TABLE 2





Compound



Compound



Compound





number
L1
L2
L3
number
L1
L2
L3
number
L1
L2
L3







 136
L101
L102
L164
190
L101
L102
L166
28
L101
L102
L145


 137
L101
L103
L164
191
L101
L103
L166
29
L101
L103
L145


 138
L101
L104
L164
192
L101
L104
L166
30
L101
L104
L145


 139
L101
L105
L164
193
L101
L105
L166
31
L101
L105
L145


 140
L101
L106
L164
194
L101
L106
L166
32
L101
L106
L145


 141
L101
L107
L164
195
L101
L107
L166
33
L101
L107
L145


 142
L101
L108
L164
196
L101
L108
L166
34
L101
L108
L145


 143
L101
L109
L164
197
L101
L109
L166
35
L101
L109
L145


 144
L101
L110
L164
198
L101
L110
L166
36
L101
L110
L145


 145
L101
L111
L164
199
L101
L111
L166
37
L101
L111
L145


 146
L101
L112
L164
200
L101
L112
L166
38
L101
L112
L145


 147
L101
L113
L164
201
L101
L113
L166
39
L101
L113
L145


 148
L101
L114
L164
202
L101
L114
L166
40
L101
L114
L145


 149
L101
L115
L164
203
L101
L115
L166
41
L101
L115
L145


 150
L101
L116
L164
204
L101
L116
L166
42
L101
L116
L145


2809
L111
L112
L174
205
L101
L117
L166
43
L101
L117
L145


2810
L111
L113
L174
206
L101
L118
L166
44
L101
L118
L145


2811
L111
L114
L174
207
L101
L119
L166
45
L101
L119
L145


2812
L111
L115
L174
208
L101
L130
L166
46
L101
L130
L145


2813
L111
L116
L174
209
L101
L131
L166
47
L101
L131
L145


2814
L111
L117
L174
210
L101
L132
L166
48
L101
L132
L145


2815
L111
L118
L174
211
L101
L133
L166
49
L101
L133
L145


2816
L111
L119
L174
212
L101
L134
L166
50
L101
L134
L145


2817
L111
L130
L174
213
L101
L140
L166
51
L101
L140
L145


2818
L111
L131
L174
214
L101
L141
L166
52
L101
L141
L145


2819
L111
L132
L174
215
L101
L159
L166
53
L101
L159
L145


2820
L111
L133
L174
216
L101
L160
L166
54
L101
L160
L145









One example of the inventive synthetic method is shown below:




where





is the precursor of ligand L1 with X being a counter ion; cis-1,2-bis(diphenylphosphino)ethylene ((z)-Bdppe)(DPPE) is the ligand L2; and Pentanodione is the ligand L3.

In describing the novel synthesis method, all reactions were carried out with rigorous exclusion of air using Schlenk-tube techniques. Solvents, except acetonitrile that was dried and distilled under argon, were obtained oxygen- and water-free from an MBraun solvent purification apparatus. 1H, 31P{1H}, 19F and 13C{1H}NMR spectra were recorded on Bruker 300 ARX, Bruker Avance 300 MHz, and Bruker Avance 400 MHz instruments. Chemical shifts (expressed in parts per million) are referenced to residual solvent peaks (1H, 13C {1H}) or external 85% H3PO4 (31P{1H}), or external CFCl3 (19F). Coupling constants J and N are given in hertz. Attenuated total reflection infrared spectra (ATR-IR) of solid samples were run on a Perkin-Elmer Spectrum 100 FT-IR spectrometer. C, H, and N analyses were carried out in a Perkin-Elmer 2400 CHNS/O analyzer. High-resolution electrospray mass spectra were acquired using a MicroTOF-Q hybrid quadrupole time-of-flight spectrometer (Bruker Daltonics, Bremen, Germany). OsH6(PiPr3)2 was prepared by the method published in Aracama, M.; Esteruelas, M. A.; Lahoz, F. J.; López, J. A.; Meyer, U.; Oro, L. A.; Werner, H. Inorg. Chem. 1991, 30, 288.
Preparation of Trihydride-Bi2




Toluene (40 mL) and NEt3 (120 μl, 0.86 mmol) were added to a mixture of the osmium precursor, OsH6(PiPr3)2 (400 mg, 0.78 mmol) and a precursor of ligand L1, 1-phenyl-3-methyl-1-H-benzimidazolium tetrafluoroborate-Bi2 (229.2 mg, 0.78 mmol). The resulting mixture was refluxed for 4 hours and then the brownish-yellow solution was extracted and concentrated under vacuum to 1 mL. MeOH was added (8 mL), affording a white powder which was filtered and washed with MeOH (2×4 mL) at 195 K and dried in vacuo.

Experimental data for trihydride-Bi2: Yield: 76.4% 426.0 mg. Analytical Calculation for C32H56N2OsP2 was C, 53.31%; H, 7.83%; N, 3.89%. Found: C, 53.01%; H, 8.14%; N, 3.91%. HRMS (electrospray, m/z): calculated for C32H51N2OsP2 [M-5H]+: 719.3295. Found: 719.3281. IR (cm−1): υ(Os—H) 2044 (m). 1H NMR (400 MHz, C6D6, 293 K): δ 8.66 (d, JH-H=7.2, 1H, CH Ph), 7.91-7.88 (m, 2H, CH Ph, CH Bzm), 7.24 (ddd, JH-H=7.2, JH-H=7.2, JH-H=1.0, 1H, CH Ph), 7.10 (ddd, JH-H=7.2, JH-H=7.2, JH-H=1.0, 1H, CH Ph), 7.05-6.99 (m, 2H, CH Bzm), 6.91 (m, 1H, CH Bzm), 3.92 (s, 3H, N—CH3), 1.79 (m, 6H, PCH), 0.96 (dvt, N=12.5, J=6.9, 18H, PCH(CH3)2) 0.83 (dvt, N=12.5, J=6.9, 18H, PCH(CH3)2), −8.18 (br, 1H, Os—H), −9.94 (br, 2H, Os—H). T1(min) (ms, OsH, 400 MHz, CD2Cl2): 118.2±10 (213 K). 13C{1H}-APT NMR, HMBC and HSQC (100.6 MHz, C6D6, 293 K): δ 206.3 (t, JC-P=5.4, NCN Bzm), 157.9 (t, JC-P=6.7, Os—C Ph), 148.9 (s, N—C Ph), 148.0 (s, C—H Ph), 137.5 (s, C Bzm), 133.6 (s, C Bzm), 124.3 (s, C—H Ph), 122.1 (s, C—H Bzm), 121.3 (s, C—H Bzm), 119.8 (s, C—H Ph), 112.5 (s, C—H Bzm), 110.4 (s, C—H Ph), 109.1 (s, C—H Bzm), 36.6 (s, N—CH3 Bzm), 27.9 (dvt, N=25.0, P—CH), 19.9 (s, PCH(CH3)2), 19.8 (s, PCH(CH3)2). 31P{1H}NMR (162.0 MHz, C6D6, 293 K): δ 25.7 (s).
Preparation of Trihydride-Bi3




Toluene (40 mL) and NEt3 (120 μl, 0.86 mmol) were added to a mixture of OsH6(PiPr3)2 (400 mg, 0.78 mmol) and 1-phenyl-3-methyl-1-H,-5,6-dimethyl-benzimidazolium tetrafluoroborate (Bi3, 250.9 mg, 0.78 mmol). The resulting mixture was refluxed for 4 hours and then the solution was extracted and concentrated under vacuum to 1 mL. MeOH was added (8 mL) and the resulting white powder was filtered and washed with MeOH (3×3 mL).
Experimental data for trihydride-Bi3: Yield: 84% 490.7 mg. Analytical Calculation for C34H60N2OsP2.CH3OH: C, 53.82%; H, 8.26%; N, 3.59%. Found: C, 53.99%; H, 8.51%; N, 3.67%. HRMS (electrospray, m/z): calculated for C34H55OsP2N2[M-H]+: 745.3452. Found: 745.3460. IR: (cm−1) υ(Os—H) 2049 (m), υ(Os—H) 2027 (m). 1H NMR (400 MHz, C6D6, 293 K): δ 8.67 (d, JH-H=7.5, 1H, CH Ph), 8.02 (dd, JH-H=7.5, JH-H=0.8, 1H, CH Ph), 7.88 (s, 1H, H Bzm), 7.24 (ddd, JH-H=7.5, JH-H=7.5, JH-H=1.1, 1H, CH Ph), 7.10 (ddd, JH-H=7.5, JH-H=7.5, JH-H=0.8, 1H, CH Ph), 6.80 (s, 1H, CH Bzm), 3.96 (s, 3H, N—CH3), 2.13 and 2.12 (both s, each 3H, —CH3 Bzm), 1.84 (m, 6H, P—CH), 0.99 (dvt, N=12.5, J=6.9, 18H, PCH(CH3)2), 0.87 (dvt, N=12.5, J=6.9, 18H, PCH(CH3)2), −8.21 (br, 1H, Os—H), −9.96 (br, 2H, Os—H). T1(min) (ms, OsH, 400 MHz, CD2Cl2): 115.0±11 (233 K). 13C{1H}-APT NMR, HMBC and HSQC (100.6 MHz, C6D6, 293 K): δ 204.9 (t, JC-P=5.6, NCN Bzm), 157.7 (t, JC-P=6.7, Os—C Ph), 149.2 (s, N—C Ph), 148.0 (s, C—H Ph), 136.2 (s, C Bzm), 132.3 (s, C Bzm), 130.3 (s, C Bzm), 129.6 (s, C Bzm), 124.2 (s, C—H Ph), 119.8 (s, C—H Ph), 112.3 (s, C—H Ph), 111.6 (s, C—H Bzm), 110.2 (s, C—H Bzm), 36.8 (s, NCH3), 28.1 (dvt, N=24.8, P—CH), 20.2 and 20.1 (both s, —CH3 Bzm), 20.0 (s, PCH(CH3)2), 19.8 (s, PCH(CH3)2). 31P{1H}NMR (162.0 MHz, C6D6, 293 K): δ 25.6 (s).
Preparation of Bisdihydrogen-Bi2




A yellow solution of trihydride-Bi2 (353.5 mg, 0.490 mmol) in Et2O (15 mL) was treated with HBF4.Et2O (87.4 μl, 0.539 mmol). The mixture was stirred for 20 minutes and the resulting brown oily product was stirred at low temperature (196 K) for 4 hours affording a white powder. The product was filtered and washed with Et2O (3×3 mL).
Experimental data for Bisdihydrogen-Bi2: Yield: 403.3 mg (83.3%). Analytical Calculation for C32H57BF4N2OsP2: C, 47.52%; H, 7.01%; N, 3.35%. Found: C, 47.37%; H, 6.87%; N, 3.42%. HRMS (electrospray, m/z): calculated for C32H51N2OsP2 [M-6H]+: 717.3138. Found: 717.3309. IR: (cm−1) υ(B—F) 1034 (br, vs). 1H NMR (300 MHz, CD2Cl2, 223 K) δ 8.10 (m, 1H, CH Bzm), 7.98 (d, JH-H=7.6, 1H, CH Ph), 7.90 (d, JH-H=7.6, 1H, CH Ph), 7.54 (m, 1H, CH Bzm), 7.45-7.42 (m, 2H, CH Bzm), 7.30 (dd, JH-H=7.6, JH-H=7.6, 1H, CH Ph), 7.01 (dd, JH-H=7.6, JH-H=7.6, 1H, CH Ph), 3.96 (s, 3H, N—CH3), 1.80 (m, 6H, P—CH), 0.86 (dvt, N=13.7, J=6.8, 18H, PCH(CH3)2), 0.81 (dvt, N=13.1, J=6.5, 18H, PCH(CH3)2), −6.74 (br, 4H, Os—H2). T1(min) (ms, OsH, 400 MHz, CD2Cl2): 12.0±2 (193 K). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2, 293 K): δ 188.6 (t, JC-P=5.6, NCN Bzm), 148.2 (Br, Os—C Ph), 144.8 (s, C—H Ph), 135.2 (s, C Bzm), 131.1 (s, C Bzm), 126.0 (s, C—H Ph), 124.4 (s, C—H Ph), 123.9 (s, C Bzm), 123.5 (s, C Bzm), 113.8 (s, C—H Ph), 111.5 (s, C—H Bzm), 111.0 (s, C—H Bzm), 36.6 (s, N—CH3), 25.4 (dvt, JP-C=13.9 Hz, P—CH), 19.3 (s, PCH(CH3)2), 18.7 (s, PCH(CH3)2). 31P{1H}NMR (121.0 MHz, CCl2D2, 293 K): δ 14.9 (s). 19F{1H}NMR (282.4 MHz, C6D6, 293 K): δ −153.3 (s).
Preparation of Bisdihydrogen-Bi3




A yellow solution of trihydride-Bi3 (100.0 mg, 0.134 mmol) in Et2O (5 mL) was treated with HBF4.Et2O (20.0 μl, 0.147 mmol). The mixture was stirred for 20 minutes and the resulting brown oily product was stirred at low temperature (196 K) for 4 hours affording a white powder. The product was filtered and washed with Et2O (3×2 mL).
Experimental data for Bisdihydrogen-Bi3: Yield: 98.3 mg (88%). Analytical Calculation for C34H61BF4N20OsP2: C, 48.8%; H, 7.35%; N, 3.35%. Found: C, 48.65%; H, 7.51%; N, 3.14%. HRMS (electrospray, m/z): calculated for C34H55N20OsP2 [M-6H]+: 745.3583. Found: 745.3452. IR: (cm−1) υ(B—F) 1048 (vs), υ(B—F) 1034 (vs). 1H NMR (300 MHz, CD2Cl2, 223 K): δ 7.98 (d, JH-H=7.5, 1H, C—H Ph), 7.89 (d, JH-H=7.5, 1H, C—H Ph), 7.85 (s, 1H, C—H Bzm), 7.34-7.25 (m, 2H, C—H Bzm and C—H Ph), 7.00 (dd, JH-H=7.5, JH-H=7.5, 1H, C—H Ph), 3.90 (s, 3H, N—CH3), 2.42 and 2.38 (both s, each 3H, —CH3, Bzm), 1.80 (m, 6H, P—CH), 0.99 (dvt, N=14.0, J=7.0, 18H, PCH(CH3)2), 0.78 (dvt, N=14.0, J=7.0, 18H, PCH(CH3)2), −6.78 (br, 4H, Os—H2). T1(min) (ms, OsH, 400 MHz, CD2Cl2): 14.2±1 (193 K). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2, 223 K): δ 187.0 (t, JC-P=7.7, NCN Bzm), 148.6 (t, J=1.6 Hz, Os—C Ph), 145.1 (s, C—H Ph), 134.0 (s, C Bzm), 133.5 (s, C Bzm), 133.2 (s, C Bzm), 129.8 (s, C Bzm), 126.1 (s, C—H Ph), 125.0 (s, C—H Ph), 114.1 (s, C—H Ph), 112.3 (s, C—H Bzm), 111.4 (s, C—H Bzm), 36.7 (s, N—CH3) 25.8 (dvt, JP-C=27.8 Hz, P—CH), 20.7 and 20.4 (both s, —CH3 Bzm), 19.6 (s, PCH(CH3)2), 18.9 (s, PCH(CH3)2). 31P{1H}NMR (121.0 MHz, CCl2D2, 293 K): δ 15.2 (s). 19F{1H}NMR (282.4 MHz, C6D6, 293 K): δ −153.3 (s).
Preparation of Bisacetonitrile-Bi2




A yellow solution of bishydrogen-Bi2 (315.0 mg, 0.376 mmol) in NCCH3 (20 mL) was stirred for 20 h under a flow of argon. The greenish-yellow solution was concentrated under vacuum to dryness and the resulting oily product was stirred in Et2O (8 mL) at 196 K. The resulting green solid was washed with Et2O (2×4 mL).
Experimental data for Bisacetonitrile-Bi2: Yield: 291.8 mg (84.7%). HRMS (electrospray, m/z): calculated for C32H51N2OsP2 [M-2H-2(NCCH3)]+: 717.3138. Found: 717.3351. IR: υ(CN, NCCH3) 2253 (w), υ(BF) 1049 (vs), υ(B—F) 1029 (vs). 1H NMR (400 MHz, CD2Cl2) δ 7.96 (m, 1H, C—H Bzm), 7.80 (d, JH-H=7.3, 1H, C—H Ph), 7.64 (d, JH-H=7.3, 1H, C—H Ph), 7.34 (m, 1H, C—H Bzm), 7.31-7.27 (m, 2H, C—H Bzm), 6.93 (dd, JH-H=7.3, JH-H=7.3, 1H, C—H Ph), 6.84 (dd, JH-H=7.3, JH-H=7.3, 1H, C—H Ph), 4.07 (s, 3H, N—CH3), 2.74 and 2.69 (both s, each 3H, NCCH3), 2.14-2.09 (m, 6H, P—CH), 0.94 (dvt, N=12.6, J=6.8, 18H, PCH(CH3)2), 0.89 (dvt, N=12.6, J=6.8, 18H, PCH(CH3)2). 13C{1H}-APT NMR, HMBC and HSQC (101 MHz, CD2Cl2) δ 188.2 (t, JC-P=7.6, NCN Bzm), 151.4 (s, C Ph), 146.6 (t, JC-P=7.7 Hz, Os—C Ph), 139.4 (s, C—H Ph), 137.5 (s, C Bzm), 133.4 (s, C Bzm), 124.8 and 123.6 (both s, NCCH3), 123.4 (br, C—H Ph and C—H Bzm), 122.4 (s, C—H Bzm), 120.6 (s, C—H Ph), 112.1 (s, C—H Ph), 110.4 (s, C—H Bzm), 109.6 (s, C—H Bzm), 35.2 (s, N—CH3), 25.1 (dvt, N=22.4, P—CH), 19.6 (s, PCH(CH3)2), 19.5 (s, PCH(CH3)2), 5.4 and 5.3 (both s, NCCH3). 31P{1H}NMR (121.0 MHz, C6D6, 293 K): δ −10.2 (s). 19F{1H}NMR (162.0 MHz, C6D6, 293 K): δ −153.3 (s).
Preparation of Bisacetonitrile-Bi3




A yellow solution of bishydrogen-Bi3 (421.8 mg, 0.504 mmol) in NCCH3 (20 mL) was stirred for 20 h under a flow of argon. The greenish-yellow solution was concentrated under vacuum to ca. 1 mL and Et2O (8 mL) was added. The resulting palish green solid was washed with Et2O (3×2 mL).
Experimental data for Bisacetonitrile-Bi3: Yield: 411.2 mg (89.2%). Analytical Calculation for C38H63BF4N4OsP2: C, 49.89; H, 6.94; N, 6.12. Found: C, 49.85; H, 6.95; N, 5.99. HRMS (electrospray, m/z): calculated for C34H55N2OsP2 [M-2H-2NCCH3]+: 745.3452. Found: 745.3489 IR: (cm−1) υ(CN, NCCH3) 2245 (w), υ(BF) 1054 (vs), υ(B—F) 1036 (vs), υ(B—F) 1025 (vs). 1H NMR (400 MHz, CD2Cl2, 298 K): δ 7.77 (d, JH-H=7.3, 1H, C—H Ph), 7.74 (s, 1H, C—H Bzm), 7.62 (d, JH-H=7.3, 1H, C—H Ph), 7.1 (s, 1H, C—H Bzm), 6.91 (dd, JH-H=7.3, JH-H=7.3, 1H, C—H Ph), 6.81 (dd, JH-H=7.3, JH-H=7.3, 1H, C—H Ph), 4.02 (s, 3H, N—CH3), 2.73 and 2.69 (both s, each 3H, NCCH3), 2.43 and 2.39 (both s, each 3H, —CH3 Bzm), 2.1 (m, 6H, P—CH), 0.93 (dvt, N=12.8, J=6.5, 18H, PCH(CH3)2), 0.89 (dvt, N=12.8, J=6.5, 18H, PCH(CH3)2). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2) δ 186.4 (t, JC-P=7.7, NCN Bzm), 151.6 (s, C Ph), 146.6 (t, JC-P=7.7 Hz, Os—C Ph), 139.3 (s, C—H Ph), 136.0 (s, C Bzm), 132.1 (s, C Bzm), 131.8 (s, C Bzm), 131.3 (s, C Bzm), 124.5 and 123.4 (both s, NCCH3), 123.1 (s, C—H Ph), 120.5 (s, C—H Ph), 111.9 (s, C—H Ph), 111.3 (s, C—H Bzm), 110.3 (s, C—H Bzm), 35.1 (s, N—CH3), 25.0 (t, JP-C=22.4, PCH), 20.6 and 20.4 (both s, —CH3 Bzm), 19.5 (s, PCH(CH3)2), 19.4 (s, PCH(CH3)2), 5.4 and 5.3 (both s, NCCH3). 31P{1H}NMR (121.0 MHz, C6D6, 293 K): δ −10.1 (s). 19F{1H}NMR (162.0 MHz, C6D6, 293 K): δ −148.2 (s).
Preparation of the Osmium Complex Compound 428
KOH (2.2 mL, 0.259 M in MeOH) was added to a solution of complex bisacetonitrile-Bi2 (300 mg, 0.338 mmol), ligand L2; cis-1,2-bis(diphenylphosphino)ethylene ((z)-Bdppe) (134.0 mg, 0.338 mmol) and ligand L3; pentanodione (58 μL, 0.58 mmol) in THF (15 mL). The resulting red solution was stirred at 323 K for 5 hours and then the solvent was concentrated under vacuum to dryness. CH2Cl2 was added and the resulting orange solution was extracted and concentrated to dryness under vacuum. The resulting yellow solid was washed with pentane (150 mL) affording a yellow powder Compound 428-1. The resulting yellowish-orange pentane solution was extracted and concentrated to dryness under vacuum affording an orange solid which was purified by chromatography (silicagel 230-400 mesh and pentane/methylene chloride 1/1 as eluent) yielding complex Compound 428-2.
Experimental Data for Compound 428-1:




Yield: 104.0 mg (34.5%). HRMS (electrospray, m/z): calculated for C45H40N2O2OsP2 [M]+: 894.2177. Found: 894.2379. IR: (cm−1) υ(CO) 1580 (m), υ(CO) 1518 (m). 1H NMR (300 MHz, CD2Cl2, 298 K): δ 8.19-6.45 (30H, 22C—H (z)-Bdppe+4C—H Bzm+4C—H Ph), 4.73 (s, 1H, C—H Acac), 2.64 (s, 3H, N—CH3), 1.50 and 1.24 (both s, each 3H, —CH3 Acac). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2): δ 189.6 (dd, JC-P=9.5, JC-P=1.6, NCN Bzm), 182.7 (s, CO Acac), 181.2 (s, CO Acac), 164.6 (dd, JP-C=85.4, JP-C=7.0, C—Os Ph), 154.6 (dd, JP-C=45.5, JP-C=32.5, C—H ethylene (z)-Bdppe), 151.0 (d, JP-C=6.7, C Ph), 150.6 (dd, JP-C=35.9, JP-C=21.8, C—H ethylene (z)-Bdppe), 139.3 (d, JP-C=33.1, C (z)-Bdppe), 138.7 (dd, JP-C=57.2, JP-C=2.6, C (z)-Bdppe), 137.9 (dd, JP-C=30.6, JP-C=1.5, C (z)-Bdppe), 137.3 (s, C Bzm), 137.3 (d, JP-C=42.8, C (z)-Bdppe), 135.4 (s, C—H Ph), 134.3 (d, JP-C=10.4, C—H (z)-Bdppe), 133.6 (s, C Bzm), 132.7 (d, JP-C=10.0, C—H (z)-Bdppe), 130.5 (d, JP-C=1.7, C—H (z)-Bdppe), 129.6 (d, JP-C=9.3, C—H (z)-Bdppe), 129.6 (br, C—H (z)-Bdppe), 129.0 (d, JP-C=9.0, C—H (z)-Bdppe), 128.3 (d, JP-C=2.0, C—H (z)-Bdppe), 128.2 (d, JP-C=0.6, C—H (z)-Bdppe). 128.0 (d, JP-C=9.6, C—H (z)-Bdppe), 127.8 (d, JP-C=7.9, C—H (z)-Bdppe), 127.5 (d, JP-C=9.7, C—H (z)-Bdppe), 123.1 (d, JP-C=4.9, C—H Ph), 121.9 (s, C—H Ph), 121.7 (s, C—H Bzm), 120.9 (s, C—H Bzm), 112.2 (d, JP-C=2.6, C—H Ph), 109.6 (s, C—H Bzm), 108.2 (s, C—H Bzm), 101.2 (s, C—H Acac), 34.9 (d, JP-C=4.7, N—CH3), 27.7 (br, 2 CH3 Acac). 31P{1H}NMR (121.0 MHz, CD2Cl2, 293 K): δ 42.7 (d, JP-P=18.5), 26.5 (d. JP-P=18.5). This complex has been characterized by X-ray diffraction analysis. The resulting X-ray molecular structure is shown in FIG. 3. Selected bond lengths (A) and angles (°) are: Os—P(1)=2.325(1), Os—P(2)=2.233(1), Os—C(1)=1.998(3), Os—C(10)=2.100(3), Os—O(1)=2.137(2), Os—O(2)=2.150(2), P(1)-Os—P(2)=83.65(3), C(1)-Os—C(10)=78.6(1), O(1)-Os—O(2)=86.19(9).
Experimental Data for Compound 428-2:




Yield 74 mg (24.6%). HRMS (electrospray, m/z): calculated for C45H41N2O2OsP2 [M]+: 894.2208. Found: 894.2177 IR: (cm−1) υ(CO) 1578 (m), υ(CO) 1512(m). 1H NMR (300 MHz, CD2Cl2, 298 K): δ 8.12 (m, 2H, C—H Ph (z)-Bdppe), 7.92 (m, 2H, C—H Ph (z)-Bdppe), 7.84-7.08 (15H, 2C—H ethylene (z)-Bdppe, 9C—H Ph (z)-Bdppe, 4C—H Bzm), 6.98 (dd, J=7.8, J=1.0, 1H, C—H Ph), 6.89 (m, 2H, C—H Ph (z)-Bdppe), 6.75 (m, 1H, C—H Ph (z)-Bdppe), 6.66 (d, JH-H=7.4, 1H, C—H Ph), 6.48 (ddd, JH-H=7.6, JH-H=7.6, JH-H=1.4, 1H, C—H Ph), 6.34 (m, 2H, C—H Ph (z)-Bdppe), 6.19 (dd, JH-H=7.4, JH-H=7.4, JH-H=1.1, 1H, C—H Ph), 6.06 (m, 2H, C—H Ph (z)-Bdppe), 5.04 (s, 1H, C—H Acac), 3.92 (s, 3H, N—CH3), 1.60 and 1.20 (both s, each 3H, —CH3 Acac). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2) δ 196.8 (dd, JP-C=104.1, JP-C=8.7, NCN Bzm), 184.2 (s, CO Acac), 183.4 (s, CO Acac), 153.8 (dd, JP-C=45.9, JP-C=28.4, C—H ethylene (z)-Bdppe), 152.6 (d, JP-C=2.2, C Ph), 147.7 (dd, JP-C=41.9, JP-C=23.4, C—H ethylene (z)-Bdppe), 145.4 (dd, JP-C=8.3, JP-C=4.3, C—Os Ph), 144.4 (d, JP-C=6.3, C—H Ph), 140.9 (d, JP-C=42.6, C Ph (z)-Bdppe), 139.2 (d, JP-C=35.3, C Ph (z) Bdppe), 137.8, (d, JP-C=35.3, C Bzm), 137 (m, C Ph (z)-Bdppe), 136.2 (d, JP-C=11.2, C—H Ph (z)-Bdppe), 135.2 (dd, JP-C=34.3, JP-C=2.4, C Ph (z)-Bdppe), 135.1 (d, JP-C=11.0, C—H Bdppe), 133.8 (d, JP-C=2.3C Bzm), 132.6 (d, JP-C=10.4, C—H Ph (z)-Bdppe), 130.5 (JP-C=1.6, C—H Ph (z)-Bdppe), 129.7-129.5 (m, 2C Ph (z)-Bdppe), 128.6 (d, JP-C=9.1, C—H Ph (z)-Bdppe), 128.2 (s, C—H Ph (z)-Bdppe), 127.8 (d, JP-C=9.5, C—H Ph (z)-Bdppe), 127.8 (d, JP-C=8.1, C—H Ph (z)-Bdppe), 127.4 (d, JP-C=2.0, C—H Ph (z)-Bdppe), 126.9 (d, JP-C=9.7, C—H Ph (z)-Bdppe), 122.8 (s, C—H Bzm), 122.7 (s, C—H Ph), 121.7 (s, C—H Bzm), 118.9 (s, C—H Ph), 111.6 (s, C—H Ph), 111.0 (s, C—H Bzm), 109.5 (s, C—H Bzm), 101.9 (s, C—H Acac), 32.1 (s, N—CH3), 28.1 (d, JP-C=4.2, —CH3 Acac), 27.6 (s, —CH3 Acac). 31P{1H}NMR (121.0 MHz, CD2Cl2, 293 K): δ 48.4 (d, JP-P=10.9), 30.6 (d. JP-P=10.9).
Preparation of Compound 1085:
KOH (4.3 mL, 0.259 M in MeOH) was added to a solution of complex bisacetonitrile-Bi3 (600 mg, 0.656 mmol), cis-1,2-bis(diphenylphosphino)ethylene ((z)-Bdppe) (259.9 mg, 0.657 mmol) and pentanodione (115 μL, 1.12 mmol) in THF (24 mL). The resulting red solution was stirred at 323 K for 3 h and then the solvent was concentrated under vacuum to dryness. CH2Cl2 was added and the resulting orange solution was extracted and concentrated to dryness under vacuum. The resulting ochre solid was washed with pentane (200 mL) affording a yellow powder (Compound 1085-1). The resulting orange pentane solution was extracted and concentrated to dryness under vacuum affording an orange solid which was purified by chromatography yielding Compound 1085-2.
Experimental Data for Compound 1085-1:




Yield: 245.2 mg (40.6%). HRMS (electrospray, m/z): calcd for C47H44N2O2OsP2 [M]+: 922.2506. found: 922.2491). IR: (cm−1) υ(CO) 1581 (m), υ(CO) 1520 (m). 1H NMR (300 MHz, CD2Cl2, 298 K): δ 8.18-6.38 (28H, 22C—H (z)-Bdppe, C—H2 Bzm, 4C—H Ph), 4.75 (s, 1H, C—H Acac), 2.57 (s, 3H, N—CH3), 2.35 and 2.22 (both s, each 3H, —CH3 Bzm), 1.50 and 1.23 (both s, each 3H, —CH3 Acac). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2): δ 188.2 (dd, JC-P=10.1, JC-P=1.5, NCN Bzm), 182.7 (s, CO Acac), 181.2 (s, CO Acac), 164.8 (dd, JP-C=85.5, JP-C=6.9, C—Os Ph), 154.8 (dd, JP-C=45.3, JP-C=32.7, C—H ethylene (z)-Bdppe), 151.3 (d, JP-C=2.2, C Ph), 150.6 (dd, JP-C=35.9, JP-C=21.9, C—H ethylene (z)-Bdppe), 139.5 (d, JP-C=32.8, C (z)-Bdppe), 139.0 (dd, JP-C=57.2, JP-C=2.5, C (z)-Bdppe), 138.1 (dd, JP-C=30.3, JP-C=1.5, C (z)-Bdppe), 137.6 (d, JP-C=42.8, C (z)-Bdppe), 135.8 (s, C Bzm), 135.5 (s, C—H Ph), 134.3 (d, JP-C=10.4, C—H (z)-Bdppe), 132.7 (d, JP-C=10.0, C—H (z)-Bdppe), 132.2 (s, C Bzm), 130.4 (d, JP-C=1.4, C—H (z)-Bdppe), 130.1 (s, C Bzm), 129.8 (d, JP-C=9.7, C—H (z)-Bdppe), 129.5 (d, JP-C=1.9, C—H (z)-Bdppe), 129.4 (s, C Bzm), 129.0 (d, JP-C=9.1, C—H (z)-Bdppe), 128.4 (d, JP-C=2.0, C—H (z)-Bdppe), 128.1 (d, JP-C=1.0, C—H (z)-Bdppe), 128.0 (d, JP-C=10.0, C—H (z)-Bdppe), 127.9 (d, JP-C=8.3C—H (z)-Bdppe), 127.6 (s, JP-C=9.7, C—H (z)-Bdppe), 122.8 (d, JP-C=5.0, C—H Ph), 121.8 (s, C—H Ph), 112.0 (d, JP-C=2.6, C—H Ph), 110.8 (s, C—H Bzm), 109.1 (s, C—H Bzm), 101.1 (s, C—H Acac), 34.83 (d, JP-C=5.0, N—CH3), 27.7 and 27.6 (both s, —CH3 Acac)), 20.49 and 20.19 (both s, —CH3 Bzm). 31P{1H}NMR (121.0 MHz, CD2Cl2, 293 K): δ 42.7 (d, JP-P=18.1), 26.6 (d. JP-P=18.1).
Experimental Data for Compound 1085-2:




Yield: 153.7 mg (25.4%). HRMS (electrospray, m/z): calculated for C47H44O2OsN2P2[M]+: 922.2506. Found: 922.2491 IR: (cm−1) υ(CO) 1581 (m), υ(CO) 1515 (m). 1H NMR (300 MHz, CD2Cl2, 298 K): δ 8.11 (m, 2H, C—H Ph (z)-Bdppe), 7.91 (m, 2H, C—H Ph (z)-Bdppe), 7.73 (ddd, JH-P=46.8, JH-P=8.7 Hz, JH-H=8.7 Hz, 1H, C—H ethylene (z)-Bdppe), 7.57-7.04 (12H, 1C—H ethylene (z)-Bdppe, 9C—H Ph (z)-Bdppe, 2C—H Bzm), 6.96 (d, J=7.4, 1H, C—H Ph), 6.89 (m, 2H, C—H Ph (z)-Bdppe), 6.76 (m, 1H, C—H Ph (z)-Bdppe), 6.62 (d, JH-H=7.4, 1H, C—H Ph), 6.45 (dd, JH-H=7.4, JH-H=7.4, 1H, C—H Ph), 6.36 (m, 2H, C—H Ph (z)-Bdppe), 6.15 (dd, JH-H=7.4, JH-H=7.4, 1H, C—H Ph), 6.07 (m, 2H, C—H Ph (z)-Bdppe), 5.02 (s, 1H, C—H Acac), 3.87 (s, 3H, N—CH3), 2.40 and 2.36 (both s, each 3H, —CH3 Bzm), 1.59 and 1.19 (both s, each 3H, —CH3 Acac). 13C{1H}-APT NMR, HMBC and HSQC (75 MHz, CD2Cl2) δ 195.6 (dd, JP-C=103.6, JP-C=7.7, NCN Bzm), 184.1 (s, CO Acac), 183.3 (s, CO Acac), 153.8 (dd, JP-C=45.7, JP-C=28.5, C—H ethylene (z)-Bdppe), 152.8 (d, JP-C=1.9, C Ph), 147.8 (dd, JP-C=41.7, JP-C=23.2, C—H ethylene (z)-Bdppe), 145.2 (dd, JP-C=7.2, JP-C=3.5, C—Os Ph), 144.4 (d, JP-C=6.2, C—H Ph), 141.1 (d, JP-C=42.5, C Ph (z)-Bdppe), 139.4 (d, JP-C=35.0, C Ph (z) Bdppe), 137.1, 136.4 and 133.5 (3C, C Bzm, 2C Ph (z)-Bdppe), 136.2 (d, JP-C=11.2, C—H Ph (z)-Bdppe), 135.1 (d, JP-C=10.9, C—H Ph (z)-Bdppe), 132.6 (d, JP-C=10.3, C—H Ph (z)-Bdppe), 132.3 (d, JP-C=2.4, C Bzm), 131.4 and 130.5 (both s, C Bzm), 130.4 (d, JP-C=1.6, C—H Ph (z)-Bdppe), 129.7 (d, JP-C=9.1, C—H Ph (z)-Bdppe), 129.6 (d, JP-C=0.6, C—H Ph (z)-Bdppe), 128.6 (d, JP-C=9.0, C—H Ph (z)-Bdppe), 128.2 (s, C—H Ph (z)-Bdppe), 127.8 (d, JP-C=9.4, C—H Ph (z)-Bdppe), 127.7 (d, JP-C=8.1, C—H Ph (z)-Bdppe), 127.3 (s, C—H Ph (z)-Bdppe), 126.9 (d, JP-C=9.6, C—H Ph (z)-Bdppe), 122.4 (s, C—H Ph), 118.8 (s, C—H Ph), 111.9 (s, C—H Bzm), 111.4 (s, C—H Ph), 110.2 (s, C—H Bzm), 101.9 (s, C—H Acac), 32.0 (s, N—CH3), 28.0 (d, JP-C=3.9, —CH3 Acac), 27.6 (s, —CH3 Acac), 20.7 and 20.5 (both s, —CH3 Bzm). 31P{1H}NMR (121.0 MHz, CD2Cl2, 293 K): δ 48.5 (d, JP-P=10.9), 30.7 (d. JP-P=10.9). This complex has been characterized by X-ray diffraction analysis. The X-ray molecular structure is shown in FIG. 4. Selected bond lengths (A) and angles (°) are: Os—P(1)=2.2270(7), Os—P(2)=2.3155(7), Os—C(1)=2.049(3), Os—C(12)=2.066(3), Os—O(1)=2.178(1), Os—O(2)=2.150(2), P(1)-Os—P(2)=83.24(3), C(1)-Os—C(12)=78.3(1), O(1)-Os—O(2)=84.57(7).
According to one aspect of the present disclosure, a compound having the formula Os(L1)(L2)(L3) is disclosed wherein L1, L2 and L3 are independently a bidentate ligand; and wherein each of L1, L2 and L3 is different from each other. In one embodiment of the compound, the ligands L1, L2 and L3 are independently selected from the group of ligands LIST-A as defined above. According to another embodiment of the compound, the ligands L1, L2 and L3 are independently selected from the group of ligands LIST-B as defined above. According to another embodiment of the compound, the ligands L1, L2 and L3 are independently selected from the group of ligands LIST-C as defined above. According to another embodiment of the compound, the ligands L1, L2 and L3 are independently selected from the group of ligands LIST-D as defined above.
According to another aspect of the present disclosure, the compound having the formula Os(L1)(L2)(L3) is selected from the group consisting of Compounds 1 to 4176 defined in Table 1 provided above. Table 2 provides a group of preferred compounds.
According to another aspect of the present disclosure, a first device comprising a first organic light emitting device is disclosed. The first organic light emitting device comprises an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer comprises a compound having the formula Os(L1)(L2)(L3), wherein L1, L2 and L3 are independently a bidentate ligand, and wherein each of L1, L2 and L3 is different from each other.
In an embodiment of the first device, the ligands L1, L2 and L3 in the compound having the formula Os(L1)(L2)(L3) are independently selected from the group of ligands LIST-A as defined above. According to another embodiment of the first device, the ligands L1, L2 and L3 in the compound having the formula Os(L1)(L2)(L3) are independently selected from the group of ligands LIST-B as defined above. According to another embodiment of the first device, the ligands L1, L2 and L3 in the compound having the formula Os(L1)(L2)(L3) are independently selected from the group of ligands LIST-C as defined above. According to another embodiment of the first device, the ligands L1, L2 and L3 in the compound having the formula Os(L1)(L2)(L3) are independently selected from the group of ligands LIST-D as defined above.
The first device can be a consumer product. The first device can be an organic light emitting device. The first device can comprise a light panel.
In another embodiment of the first device, the organic layer is an emissive layer and the compound is an emissive dopant. In another embodiment, the compound is a non-emissive dopant in the emissive layer.
In another embodiment of the first device, the organic layer further comprises a host material. The host material can comprise a triphenylene containing benzo-fused thiophene or benzo-fused furan; wherein any substituent in the host material is an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1—Ar2, CnH2n—Ar1, or no substitution;
wherein n is from 1 to 10; and
wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In another embodiment, the host material comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
In another embodiment, the host material is selected from the group consisting of







and combinations thereof.

In yet another embodiment, the host material comprises a metal complex.
According to another aspect of the present disclosure, a novel formulation is disclosed. The formulation comprises a compound having a structure according to the formula Os(L1)(L2)(L3), wherein L1, L2 and L3 are independently a bidentate ligand, and wherein each of L1, L2 and L3 is different from each other.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:




Each of Ar1 to Ar9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:




wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:




wherein Met is a metal, which can have an atomic weight greater than 40; (Y101—Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k′′ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y101—Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101—Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:




wherein Met is a metal; (Y103—Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k′′ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:




wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103—Y104) is a carbene ligand.
Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, host compound contains at least one of the following groups in the molecule:







wherein R101 to R107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′′′ is an integer from 0 to 20. X101 to X108 is selected from C (including CH) or N. Z101 and Z102 is selected from NR101, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:




wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:




wherein R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:




wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 3 below. Table 3 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.









TABLE 3





MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS















Hole injection materials









Phthalocyanine and porphryin compounds




Appl. Phys. Lett. 69, 2160 (1996)


 


Starburst triarylamines




J. Lumin. 72-74, 985 (1997)


 


CFx Fluorohydrocarbon polymer




Appl. Phys. Lett. 78, 673 (2001)


 


Conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene)




Synth. Met. 87, 171 (1997) WO2007002683


 


Phosphonic acid and silane SAMs




US20030162053


 


Triarylamine or polythiophene polymers with conductivity dopants




EP1725079A1


 










 










 


Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides      




US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 


 


n-type semiconducting organic complexes




US20020158242


 


Metal organometallic complexes




US20060240279


 


Cross-linkable compounds




US20080220265


 


Polythiophene based polymers and copolymers




WO 2011075644 EP2350216


 







Hole transporting materials









Triarylamines (e.g., TPD, α-NPD)




Appl. Phys. Lett. 51, 913 (1987)


 







U.S. Pat. No. 5,061,569


 







EP650955


 







J. Mater. Chem. 3, 319 (1993)


 







Appl. Phys. Lett. 90, 183503 (2007)


 







Appl. Phys. Lett. 90, 183503 (2007)


 


Triaylamine on spirofluorene core




Synth. Met. 91, 209 (1997)


 


Arylamine carbazole compounds




Adv. Mater. 6, 677 (1994), US20080124572


 


Triarylamine with (di)benzothiophene/ (di)benzofuran




US20070278938, US20080106190 US20110163302


 


Indolocarbazoles




Synth. Met. 111, 421 (2000)


 


Isoindole compounds




Chem. Mater. 15, 3148 (2003)


 


Metal carbene complexes




US20080018221


 







Phosphorescent OLED host materials


Red hosts









Arylcarbazoles




Appl. Phys. Lett. 78, 1622 (2001)


 


Metal 8-hydroxyquinolates (e.g., Alq3, BAlq)




Nature 395, 151 (1998)


 







US20060202194


 







WO2005014551


 







WO2006072002


 


Metal phenoxybenzothiazole compounds




Appl. Phys. Lett. 90, 123509 (2007)


 


Conjugated oligomers and polymers (e.g., polyfluorene)




Org. Electron. 1, 15 (2000)


 


Aromatic fused rings




WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065


 


Zinc complexes




WO2010056066


 


Chrysene based compounds




WO2011086863


 







Green hosts









Arylcarbazoles




Appl. Phys. Lett. 78, 1622 (2001)


 







US20030175553


 







WO2001039234


 


Aryltriphenylene compounds




US20060280965


 







US20060280965


 







WO2009021126


 


Poly-fused heteroaryl compounds




US20090309488 US20090302743 US20100012931


 


Donor acceptor type molecules




WO2008056746


 







WO2010107244


 


Aza- carbazole/DBT/DBF




JP2008074939


 







US20100187984


 


Polymers (e.g., PVK)




Appl. Phys. Lett. 77, 2280 (2000)


 


Spirofluorene compounds




WO2004093207


 


Metal phenoxybenzooxazole compounds




WO2005089025


 







WO2006132173


 







JP200511610


 


Spirofluorene- carbazole compounds




JP2007254297


 







JP2007254297


 


Indolocabazoles




WO2007063796


 







WO2007063754


 


5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)




J. Appl. Phys. 90, 5048 (2001)


 







WO2004107822


 


Tetraphenylene complexes




US20050112407


 


Metal phenoxypyridine compounds




WO2005030900


 


Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)




US20040137268, US20040137267


 







Blue hosts









Arylcarbazoles




Appl. Phys. Lett, 82, 2422 (2003)


 







US20070190359


 


Dibenzothiophene/ Dibenzofuran- carbazole compounds




WO2006114966, US20090167162


 







US20090167162


 







WO2009086028


 







US20090030202, US20090017330


 







US20100084966


 


Silicon aryl compounds




US20050238919


 







WO2009003898


 


Silicon/Germanium aryl compounds




EP2034538A


 


Aryl benzoyl ester




WO2006100298


 


Carbazole linked by non-conjugated groups




US20040115476


 


Aza-carbazoles




US20060121308


 


High triplet metal organometallic complex




U.S. Pat. No. 7,154,114


 







Phosphorescent dopants


Red dopants









Heavy metal porphyrins (e.g., PtOEP)




Nature 395, 151 (1998)


 


Iridium(III) organometallic complexes




Appl. Phys. Lett. 78, 1622 (2001)


 







US2006835469


 







US2006835469


 







US20060202194


 







US20060202194


 







US20070087321


 







US20080261076 US20100090591


 







US20070087321


 







Adv. Mater. 19, 739 (2007)


 







WO2009100991


 







WO2008101842


 







U.S. Pat. No. 7,232,618


 


Platinum(II) organometallic complexes




WO2003040257


 







US20070103060


 


Osminum(III) complexes




Chem. Mater. 17, 3532 (2005)


 


Ruthenium(II) complexes




Adv. Mater. 17, 1059 (2005)


 


Rhenium (I), (II), and (III) complexes




US20050244673


 







Green dopants









Iridium(III) organometallic complexes




Inorg. Chem. 40, 1704 (2001)


 







US20020034656


 







U.S. Pat. No. 7,332,232


 







US20090108737


 







WO2010028151


 







EP1841834B


 







US20060127696


 







US20090039776


 







U.S. Pat. No. 6,921,915


 







US20100244004


 







U.S. Pat. No. 6,687,266


 







Chem. Mater. 16, 2480 (2004)


 







US20070190359


 







US 20060008670 JP2007123392


 







WO2010086089, WO2011044988


 







Adv. Mater. 16, 2003 (2004)


 







Angew. Chem. Int. Ed. 2006, 45, 7800


 







WO2009050290


 







US20090165846


 







US20080015355


 







US20010015432


 







US20100295032


 


Monomer for polymeric metal organometallic compounds




U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598


 


Pt(II) organometallic complexes, including polydentated ligands




Appl. Phys. Lett. 86, 153505 (2005)


 







Appl. Phys. Lett. 86, 153505 (2005)


 







Chem. Lett. 34, 592 (2005)


 







WO2002015645


 







US20060263635


 







US20060182992 US20070103060


 


Cu complexes




WO2009000673


 







US20070111026


 


Gold complexes




Chem. Commun. 2906 (2005)


 


Rhenium(III) complexes




Inorg. Chem. 42, 1248 (2003)


 


Osmium(II) complexes




U.S. Pat. No. 7,279,704


 


Deuterated organometallic complexes




US20030138657


 


Organometallic complexes with two or more metal centers




US20030152802


 







U.S. Pat. No. 7,090,928


 







Blue dopants









Iridium(III) organometallic complexes




WO2002002714


 







WO2006009024


 







US20060251923 US20110057559 US20110204333


 







U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373


 







U.S. Pat. No. 7,534,505


 







WO2011051404


 







U.S. Pat. No. 7,445,855


 







US20070190359, US20080297033 US20100148663


 







U.S. Pat. No. 7,338,722


 







US20020134984


 







Angew. Chem. Int. Ed. 47, 4542 (2008)


 







Chem. Mater. 18, 5119 (2006)


 







Inorg. Chem. 46, 4308 (2007)


 







WO2005123873


 







WO2005123873


 







WO2007004380


 







WO2006082742


 


Osmium(II) complexes




U.S. Pat. No. 7,279,704


 







Organometallics 23, 3745 (2004)


 


Gold complexes




Appl. Phys. Lett. 74, 1361 (1999)


 


Platinum(II) complexes




WO2006098120, WO2006103874


 


Pt tetradentate complexes with at least one metal- carbene bond




U.S. Pat. No. 7,655,323


 







Exciton/hole blocking layer materials









Bathocuprine compounds (e.g., BCP, BPhen)




Appl. Phys. Lett. 75, 4 (1999)


 







Appl. Phys. Lett. 79, 449 (2001)


 


Metal 8-hydroxyquinolates (e.g., BAlq)




Appl. Phys. Lett. 81, 162 (2002)


 


5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole




Appl. Phys. Lett. 81, 162 (2002)


 


Triphenylene compounds




US20050025993


 


Fluorinated aromatic compounds




Appl. Phys. Lett. 79, 156 (2001)


 


Phenothiazine-S-oxide




WO2008132085


 


Silylated five- membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles




WO2010079051


 


Aza-carbazoles




US20060121308


 







Electron transporting materials









Anthracene- benzoimidazole compounds




WO2003060956


 







US20090179554


 


Aza triphenylene derivatives




US20090115316


 


Anthracene- benzothiazole compounds




Appl. Phys. Lett. 89, 063504 (2006)


 


Metal 8-hydroxyquinolates (e.g., Alq3, Zrq4)




Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107


 


Metal hydroxybenoquinolates




Chem. Lett. 5, 905 (1993)


 


Bathocuprine compounds such as BCP, BPhen, etc




Appl. Phys. Lett. 91, 263503 (2007)


 







Appl. Phys. Lett. 79, 449 (2001)


 


5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)




Appl. Phys. Lett. 74, 865 (1999)


 







Appl. Phys. Lett. 55, 1489 (1989)


 







Jpn. J. Apply. Phys. 32, L917 (1993)


 


Silole compounds




Org. Electron. 4, 113 (2003)


 


Arylborane compounds




J. Am. Chem. Soc. 120, 9714 (1998)


 


Fluorinated aromatic compounds




J. Am. Chem. Soc. 122, 1832 (2000)


 


Fullerene (e.g., C60)




US20090101870


 


Triazine complexes




US20040036077


 


Zn (N{circumflex over ( )}N) complexes




U.S. Pat. No. 6,528,187









It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

## Claims

1. A method of making a compound having the formula Os(L1)(L2)(L3), wherein each of L1, L2, and L3 is independently a bidentate ligand, said method comprising:
(a) reacting a precursor of ligand L1 with an osmium precursor to form a first intermediate product that has the ligand L1 coordinated to the osmium, wherein the osmium precursor has the formula OsHx(PR3)y, wherein x is an integer from 2 to 6 and y is an integer from 2 to 5, and R is selected from the group consisting of aryl, alkyl and cycloalkyl;
(b) reacting the first intermediate product with a reducing agent to form a Os(II) second intermediate product;
(c) reacting the second intermediate product with a coordinating solvent to form a third intermediate product; and
(d) reacting a mixture of precursors of ligands L2 and L3 with said third intermediate product;
wherein L1 is




wherein one of L2 and L3 is




wherein the other of L2 and L3 is





and
wherein C is a monoanionic carbon coordinating atom, C′ is a neutral carbene coordinating atom, P and P′ are each a neutral phosphorus coordinating atom, O is a monoanionic oxygen coordinating atom, and O′ is a neutral oxygen coordinating atom.

2. A compound having the formula Os(L1)(L2)(L3):
wherein L1, L2 and L3 are independently a bidentate ligand;
wherein L1 is




wherein one of L2 and L3 is




wherein the other of L2 and L3 is





and
wherein C is a monoanionic carbon coordinating atom, C′ is a neutral carbene coordinating atom, P and P′ are each a neutral phosphorus coordinating atom, O is a monoanionic oxygen coordinating atom, and O′ is a neutral oxygen coordinating atom.

3. A first device comprising a first organic light emitting device, the first organic light emitting device comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having the formula Os(L1)(L2)(L3),
wherein L1, L2 and L3 are independently a bidentate ligand,
wherein L1 is




wherein one of L2 and L3 is




wherein the other of L2 and L3 is





and
wherein C is a monoanionic carbon coordinating atom, C′ is a neutral carbene coordinating atom, P and P′ are each a neutral phosphorus coordinating atom, O is a monoanionic oxygen coordinating atom, and O′ is a neutral oxygen coordinating atom.

4. The first device of claim 3, wherein the first device is a consumer product.

5. The first device of claim 3, wherein the first device is an organic light emitting device.

6. The first device of claim 3, wherein the first device comprises a light panel.

7. The first device of claim 3, wherein the organic layer is an emissive layer and the compound is an emissive dopant.

8. The first device of claim 3, wherein the organic layer is an emissive layer and the compound is a non-emissive dopant.

9. The first device of claim 3, wherein the organic layer further comprises a host material.

10. The compound of claim 2, wherein L1 is



wherein L3 is




wherein Ra, Rb and Rc are each independently no substitutions, up to the maximum possible substitutions;
wherein Ra, Rb, and Rc, are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein two adjacent substituents of Ra, Rb, and Rc are optionally joined to form a fused ring and may be further substituted; and
wherein the dash lines show the connection points to osmium.

11. The compound of claim 2, wherein L1 is selected from the group consisting of:












wherein the dash lines show the connection points to osmium.

12. The compound of claim 11, wherein the compound is selected from the group consisting of:













Compound





number
L1
L2
L3


















26.
L101
L159
L144


53.
L101
L159
L145


80.
L101
L159
L147


376.
L102
L159
L144


402.
L102
L159
L145


428.
L102
L159
L147


713.
L103
L159
L144


738.
L103
L159
L145


763.
L103
L159
L147


1037.
L104
L159
L144


1061.
L104
L159
L145


1085.
L104
L159
L147


1348.
L105
L159
L144


1371.
L105
L159
L145


1394.
L105
L159
L147


1646.
L106
L159
L144


1668.
L106
L159
L145


1690.
L106
L159
L147


1931.
L107
L159
L144


1952.
L107
L159
L145


1973.
L107
L159
L147


2203.
L108
L159
L144


2223.
L108
L159
L145


2243.
L108
L159
L147


2462.
L109
L159
L144


2481.
L109
L159
L145


2500.
L109
L159
L147


2708.
L110
L159
L144


2726.
L110
L159
L145


2744.
L110
L159
L147


2941.
L111
L159
L144


2958.
L111
L159
L145


2705.
L111
L159
L147


2891.
L112
L159
L144


2907.
L112
L159
L145


2923.
L112
L159
L147


3098.
L113
L159
L144


3113.
L113
L159
L145


3128.
L113
L159
L147


3292.
L114
L159
L144


3306.
L114
L159
L145


3320.
L114
L159
L147


3473.
L115
L159
L144


3486.
L115
L159
L145


3499.
L115
L159
L147


3653.
L116
L159
L145


3665.
L116
L159
L147


3796.
L117
L159
L144


3807.
L117
L159
L145


3818.
L117
L159
L147


3938.
L118
L159
L144


3948.
L118
L159
L145


3958.
L118
L159
L147


4067.
L119
L159
L144


4076.
L119
L159
L145


4085.
L119
L159
L147









wherein L144 to L145, L147, and L159 have the following meanings:




wherein the dash lines show the connection points to osmium.

13. The compound of claim 2, wherein L2 s elected from the group consisting of:



wherein the dash lines show the connection points to osmium.

14. The first device of claim 3, wherein L1 is




and
wherein L3 is




wherein Ra, Rb and Rc are each independently no substitutions, up to the maximum possible substitutions;
wherein Ra, Rb, and Rc, are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein two adjacent substituents of Ra, Rb, and Rc are optionally joined to form a fused ring and may be further substituted; and
wherein the dash lines show the connection points to osmium.

15. The first device of claim 3, wherein L1 is selected from the group consisting of:












wherein the dash lines show the connection points to osmium.

16. The first device of claim 15, wherein the compound is selected from the group consisting of:













Compound





number
L1
L2
L3


















26.
L101
L159
L144


53.
L101
L159
L145


80.
L101
L159
L147


376.
L102
L159
L144


402.
L102
L159
L145


428.
L102
L159
L147


713.
L103
L159
L144


738.
L103
L159
L145


763.
L103
L159
L147


1037.
L104
L159
L144


1061.
L104
L159
L145


1085.
L104
L159
L147


1348.
L105
L159
L144


1371.
L105
L159
L145


1394.
L105
L159
L147


1646.
L106
L159
L144


1668.
L106
L159
L145


1690.
L106
L159
L147


1931.
L107
L159
L144


1952.
L107
L159
L145


1973.
L107
L159
L147


2203.
L108
L159
L144


2223.
L108
L159
L145


2243.
L108
L159
L147


2462.
L109
L159
L144


2481.
L109
L159
L145


2500.
L109
L159
L147


2708.
L110
L159
L144


2726.
L110
L159
L145


2744.
L110
L159
L147


2941.
L111
L159
L144


2958.
L111
L159
L145


2705.
L111
L159
L147


2891.
L112
L159
L144


2907.
L112
L159
L145


2923.
L112
L159
L147


3098.
L113
L159
L144


3113.
L113
L159
L145


3128.
L113
L159
L147


3292.
L114
L159
L144


3306.
L114
L159
L145


3320.
L114
L159
L147


3473.
L115
L159
L144


3486.
L115
L159
L145


3499.
L115
L159
L147


3653.
L116
L159
L145


3665.
L116
L159
L147


3796.
L117
L159
L144


3807.
L117
L159
L145


3818.
L117
L159
L147


3938.
L118
L159
L144


3948.
L118
L159
L145


3958.
L118
L159
L147


4067.
L119
L159
L144


4076.
L119
L159
L145


4085.
L119
L159
L147









wherein L144 to L145, L147, and L159 have the following meanings:




wherein the dash lines show the connection points to osmium.

17. The first device of claim 3, wherein L2 is selected from the group consisting of:



wherein the dash lines show the connection points to osmium.