# Patent

## Title
Organic electronuminescent materials and devices

## Abstract

Novel iridium complexes containing phenylpyridine and pyridyl aza-benzo fused ligands are described. These complexes are useful as light emitters when incorporated into OLEDs.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of U.S. application Ser. No. 13/673,338, filed Nov. 9, 2012, the disclosure of which is expressly incorporated herein by reference in its entirety.


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, The 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 iridium complexes containing aza-benzo fused ligands. In particular, iridium complexes containing both phenylpyridine ligands and aza-benzo fused ligands were found to be useful as phosphorescent emitters when used in OLED devices. Additionally, iridium complexes containing both phenylpyridine ligands and aza-benzo fused ligands where an alkyl group is bonded to the pyridine ring of the aza-dibenzofuran moiety of the ligand were also found to be useful as phosphorescent emitters.
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 OF THE INVENTION
A compound having the formula Ir(LA)n(LB)3-n, and having the structure:




with Formula I is provided. In the compound of Formula I, A1, A2, A3, A4, A5, A6, A7, and A8 comprise carbon or nitrogen, and at least one of A1, A2, A3, A4, A5, A6, A7, and A8 is nitrogen. Ring B is bonded to ring A through a C—C bond, the iridium is bonded to ring A through a Ir—C bond. X is O, S, or Se. R1, R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution, and any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring. R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.

In one aspect, n is 1. In one aspect, the compound has the formula:




In one aspect, the compound has the formula:




In one aspect, only one of A1 to A8 is nitrogen. In one aspect, only one of A5 to A8 is nitrogen. In one aspect, X is O.
In one aspect, R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof. In one aspect, R2 is alkyl.
In one aspect, the alkyl is deuterated or partially deuterated. In one aspect, R3 is alkyl.
In one aspect, the alkyl is deuterated or partially deuterated.
In one embodiment, a first device comprising a first organic light emitting device is provided. The first device further 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 Ir(LA)n(LB)3-n, having the structure according to Formula I.
The inventors have found that iridium complexes containing aza-benzo fused ligands, I particular iridium complexes containing both phenylpyridine ligands and aza-benzo fused ligands are useful as phosphorescent emitters useful for OLED devices.
According to another aspect of the present disclosure, a compound having the formula Ir(LA)n(LB)3-n, and having the structure:




Formula II, is provided. In the compound of Formula II, X is O, S, or Se; R is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; R1 represent mono-, di-substitution, or no substitution; R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution; any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring; R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.

According to an embodiment, a first device comprising a first organic light emitting device, further comprising an anode, a cathode, and an organic layer, disposed between the anode and the cathode, comprising a compound having the formula Ir(LA)n(LB)3-n, and having the structure according to Formula II is disclosed.
The inventors have discovered that addition of an alkyl group to the aza ring of the specific aza-dibenzofuran ring system in the iridium complexes containing aza-benzo fused ligands results in the formation of green phosphorescent compounds with superior device stability.



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 show structural Formula I and Formula II.



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, 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.).
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, arylkyl, 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.
A compound having the formula Ir(LA)n(LB)3-n, and having the structure:




with Formula I is provided. In the compound of Formula I, A1, A2, A3, A4, A5, A6, A7, and A8 comprise carbon or nitrogen, and at least one of A1, A2, A3, A4, A5, A6, A7, and A8 is nitrogen. Ring B is bonded to ring A through a C—C bond, the iridium is bonded to ring A through a Ir—C bond. X is O, S, or Se. R1, R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution, and any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring. R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.

Heteroleptic iridium complexes with 2-phenylpyridine and 2-(4-dibenzofuran)-pyridine ligands have been previously disclosed. The dibenzofuran substitution extends the conjugation of the ligand and lowers the LUMO of the complex, resulting in a slight red shifted emission and less saturated green color. For example, Compound A has a λmax of 528 nm in 2-methyl-tetrahydrofuran at room temperature, compared to around 516 nm for tris(2-phenylpyridine)iridium. The compounds of Formula I introduce an azadibenzofuran substitution, as in, for example, Compound 1, which further lowers the LUMO of the complex due to the electron deficient nature of the azadibenzofuran group. The reduction potential was measured at −2.55 V versus −2.60 V for Compound A. Based on these results, it was expected that the emission of Compound 1 will be further red shifted. Surprisingly, the PL of compounds of Formula I such as Compound 1, measured under the same condition as Compound A, showed a λmax of 523 nm, which is 5 nm blue shifted compared to Compound A. Similarly, the λmax of Compound 4 is 524 nm which is 4 nm blue shifted compared to Compound A. The results are summarized in Table 1. Thus, compounds of Formula I unexpectedly have blue shifted emission spectra, which makes compounds of Formula I more suitable for use as a saturated green color in display applications.










TABLE 1







Redox
PL (phosphorescent




Potential vs.
luminescence) in 2-


Compound
Structure
Fc/Fc+
methyl-THF







Ir(PPy)3




ERed: −2.70 V EOx: 0.31 V
R.T.: 516 nm 77 K: 493 nm


 


Compound A




ERed: −2.60 V EOx: 0.35 V
R.T.: 528 nm 77 K: 512 nm


 


Compound 1




ERed: −2.55 V EOx: 0.40 V
R.T.: 523 nm 77 K: 510 nm


 


Compound 4




ERed: −2.55 V Eox: 0.37 V
R.T.: 524 nm 77 K: 510









In one embodiment, n is 1. In one embodiment, the compound has the formula:




In one embodiment, the compound has the formula:




In one embodiment, only one of A1 to A8 is nitrogen. In one embodiment, only one of A5 to A8 is nitrogen. In one embodiment, X is O.
In one embodiment, R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof. In one embodiment, R2 is alkyl.
In one embodiment, the alkyl is deuterated or partially deuterated. In one embodiment, R3 is alkyl.
In one embodiment, the alkyl is deuterated or partially deuterated.
In one embodiment, LA is selected from the group consisting of:





























































In one embodiment, LA is selected from the group consisting of:













In one embodiment, LB is selected from the group consisting of:










In one embodiment, the compound of formula Ir(LA)(LB)2 has one of the formulas listed in the table below:












Compound




Number
LA
LB

















1.
LA1
LB1


2.
LA2
LB1


3.
LA3
LB1


4.
LA4
LB1


5.
LA5
LB1


6.
LA6
LB1


7.
LA7
LB1


8.
LA8
LB1


9.
LA9
LB1


10.
LA10
LB1


11.
LA11
LB1


12.
LA12
LB1


13.
LA13
LB1


14.
LA14
LB1


15.
LA15
LB1


16.
LA16
LB1


17.
LA17
LB1


18.
LA18
LB1


19.
LA19
LB1


20.
LA10
LB1


21.
LA21
LB1


22.
LA22
LB1


23.
LA23
LB1


24.
LA24
LB1


25.
LA25
LB1


26.
LA26
LB1


27.
LA27
LB1


28.
LA28
LB1


29.
LA29
LB1


30.
LA30
LB1


31.
LA31
LB1


32.
LA32
LB1


33.
LA33
LB1


34.
LA34
LB1


35.
LA35
LB1


36.
LA36
LB1


37.
LA37
LB1


38.
LA38
LB1


39.
LA39
LB1


40.
LA40
LB1


41.
LA41
LB1


42.
LA42
LB1


43.
LA43
LB1


44.
LA44
LB1


45.
LA45
LB1


46.
LA46
LB1


47.
LA47
LB1


48.
LA48
LB1


49.
LA49
LB1


50.
LA50
LB1


51.
LA51
LB1


52.
LA52
LB1


53.
LA53
LB1


54.
LA54
LB1


55.
LA55
LB1


56.
LA56
LB1


57.
LA57
LB1


58.
LA58
LB1


59.
LA59
LB1


60.
LA60
LB1


61.
LA61
LB1


62.
LA62
LB1


63.
LA63
LB1


64.
LA64
LB1


65.
LA65
LB1


66.
LA66
LB1


67.
LA67
LB1


68.
LA68
LB1


69.
LA69
LB1


70.
LA70
LB1


71.
LA71
LB1


72.
LA72
LB1


73.
LA73
LB1


74.
LA74
LB1


75.
LA75
LB1


76.
LA76
LB1


77.
LA77
LB1


78.
LA78
LB1


79.
LA79
LB1


80.
LA80
LB1


81.
LA81
LB1


82.
LA82
LB1


83.
LA83
LB1


84.
LA84
LB1


85.
LA85
LB1


86.
LA86
LB1


87.
LA87
LB1


88.
LA88
LB1


89.
LA89
LB1


90.
LA90
LB1


91.
LA91
LB1


92.
LA92
LB1


93.
LA93
LB1


94.
LA94
LB1


95.
LA95
LB1


96.
LA96
LB1


97.
LA97
LB1


98.
LA98
LB1


99.
LA99
LB1


100.
LA100
LB1


101.
LA101
LB1


102.
LA102
LB1


103.
LA103
LB1


104.
LA104
LB1


105.
LA105
LB1


106.
LA106
LB1


107.
LA107
LB1


108.
LA108
LB1


109.
LA109
LB1


110.
LA110
LB1


111.
LA111
LB1


112.
LA112
LB1


113.
LA113
LB1


114.
LA114
LB1


115.
LA115
LB1


116.
LA116
LB1


117.
LA117
LB1


118.
LA118
LB1


119.
LA119
LB1


120.
LA1
LB2


121.
LA2
LB2


122.
LA3
LB2


123.
LA4
LB2


124.
LA5
LB2


125.
LA6
LB2


126.
LA7
LB2


127.
LA8
LB2


128.
LA9
LB2


129.
LA10
LB2


130.
LA11
LB2


131.
LA12
LB2


132.
LA13
LB2


133.
LA14
LB2


134.
LA15
LB2


135.
LA16
LB2


136.
LA17
LB2


137.
LA18
LB2


138.
LA19
LB2


139.
LA10
LB2


140.
LA21
LB2


141.
LA22
LB2


142.
LA23
LB2


143.
LA24
LB2


144.
LA25
LB2


145.
LA26
LB2


146.
LA27
LB2


147.
LA28
LB2


148.
LA29
LB2


149.
LA30
LB2


150.
LA31
LB2


151.
LA32
LB2


152.
LA33
LB2


153.
LA34
LB2


154.
LA35
LB2


155.
LA36
LB2


156.
LA37
LB2


157.
LA38
LB2


158.
LA39
LB2


159.
LA40
LB2


160.
LA41
LB2


161.
LA42
LB2


162.
LA43
LB2


163.
LA44
LB2


164.
LA45
LB2


165.
LA46
LB2


166.
LA47
LB2


167.
LA48
LB2


168.
LA49
LB2


169.
LA50
LB2


170.
LA51
LB2


171.
LA52
LB2


172.
LA53
LB2


173.
LA54
LB2


174.
LA55
LB2


175.
LA56
LB2


176.
LA57
LB2


177.
LA58
LB2


178.
LA59
LB2


179.
LA60
LB2


180.
LA61
LB2


181.
LA62
LB2


182.
LA63
LB2


183.
LA64
LB2


184.
LA65
LB2


185.
LA66
LB2


186.
LA67
LB2


187.
LA68
LB2


188.
LA69
LB2


189.
LA70
LB2


190.
LA71
LB2


191.
LA72
LB2


192.
LA73
LB2


193.
LA74
LB2


194.
LA75
LB2


195.
LA76
LB2


196.
LA77
LB2


197.
LA78
LB2


198.
LA79
LB2


199.
LA80
LB2


200.
LA81
LB2


201.
LA82
LB2


202.
LA83
LB2


203.
LA84
LB2


204.
LA85
LB2


205.
LA86
LB2


206.
LA87
LB2


207.
LA88
LB2


208.
LA89
LB2


209.
LA90
LB2


210.
LA91
LB2


211.
LA92
LB2


212.
LA93
LB2


213.
LA94
LB2


214.
LA95
LB2


215.
LA96
LB2


216.
LA97
LB2


217.
LA98
LB2


218.
LA99
LB2


219.
LA100
LB2


220.
LA101
LB2


221.
LA102
LB2


222.
LA103
LB2


223.
LA104
LB2


224.
LA105
LB2


225.
LA106
LB2


226.
LA107
LB2


227.
LA108
LB2


228.
LA109
LB2


229.
LA110
LB2


230.
LA111
LB2


231.
LA112
LB2


232.
LA113
LB2


233.
LA114
LB2


234.
LA115
LB2


235.
LA116
LB2


236.
LA117
LB2


237.
LA118
LB2


238.
LA119
LB2


239.
LA1
LB3


240.
LA2
LB3


241.
LA3
LB3


242.
LA4
LB3


243.
LA5
LB3


244.
LA6
LB3


245.
LA7
LB3


246.
LA8
LB3


247.
LA9
LB3


248.
LA10
LB3


249.
LA11
LB3


250.
LA12
LB3


251.
LA13
LB3


252.
LA14
LB3


253.
LA15
LB3


254.
LA16
LB3


255.
LA17
LB3


256.
LA18
LB3


257.
LA19
LB3


258.
LA10
LB3


259.
LA21
LB3


260.
LA22
LB3


261.
LA23
LB3


262.
LA24
LB3


263.
LA25
LB3


264.
LA26
LB3


265.
LA27
LB3


266.
LA28
LB3


267.
LA29
LB3


268.
LA30
LB3


269.
LA31
LB3


270.
LA32
LB3


271.
LA33
LB3


272.
LA34
LB3


273.
LA35
LB3


274.
LA36
LB3


275.
LA37
LB3


276.
LA38
LB3


277.
LA39
LB3


278.
LA40
LB3


279.
LA41
LB3


280.
LA42
LB3


281.
LA43
LB3


282.
LA44
LB3


283.
LA45
LB3


284.
LA46
LB3


285.
LA47
LB3


286.
LA48
LB3


287.
LA49
LB3


288.
LA50
LB3


289.
LA51
LB3


290.
LA52
LB3


291.
LA53
LB3


292.
LA54
LB3


293.
LA55
LB3


294.
LA56
LB3


295.
LA57
LB3


296.
LA58
LB3


297.
LA59
LB3


298.
LA60
LB3


299.
LA61
LB3


300.
LA62
LB3


301.
LA63
LB3


302.
LA64
LB3


303.
LA65
LB3


304.
LA66
LB3


305.
LA67
LB3


306.
LA68
LB3


307.
LA69
LB3


308.
LA70
LB3


309.
LA71
LB3


310.
LA72
LB3


311.
LA73
LB3


312.
LA74
LB3


313.
LA75
LB3


314.
LA76
LB3


315.
LA77
LB3


316.
LA78
LB3


317.
LA79
LB3


318.
LA80
LB3


319.
LA81
LB3


320.
LA82
LB3


321.
LA83
LB3


322.
LA84
LB3


323.
LA85
LB3


324.
LA86
LB3


325.
LA87
LB3


326.
LA88
LB3


327.
LA89
LB3


328.
LA90
LB3


329.
LA91
LB3


330.
LA92
LB3


331.
LA93
LB3


332.
LA94
LB3


333.
LA95
LB3


334.
LA96
LB3


335.
LA97
LB3


336.
LA98
LB3


337.
LA99
LB3


338.
LA100
LB3


339.
LA101
LB3


340.
LA102
LB3


341.
LA103
LB3


342.
LA104
LB3


343.
LA105
LB3


344.
LA106
LB3


345.
LA107
LB3


346.
LA108
LB3


347.
LA109
LB3


348.
LA110
LB3


349.
LA111
LB3


350.
LA112
LB3


351.
LA113
LB3


352.
LA114
LB3


353.
LA115
LB3


354.
LA116
LB3


355.
LA117
LB3


356.
LA118
LB3


357.
LA119
LB3


358.
LA1
LB4


359.
LA2
LB4


360.
LA3
LB4


361.
LA4
LB4


362.
LA5
LB4


363.
LA6
LB4


364.
LA7
LB4


365.
LA8
LB4


366.
LA9
LB4


367.
LA10
LB4


368.
LA11
LB4


369.
LA12
LB4


370.
LA13
LB4


371.
LA14
LB4


372.
LA15
LB4


373.
LA16
LB4


374.
LA17
LB4


375.
LA18
LB4


376.
LA19
LB4


377.
LA10
LB4


378.
LA21
LB4


379.
LA22
LB4


380.
LA23
LB4


381.
LA24
LB4


382.
LA25
LB4


383.
LA26
LB4


384.
LA27
LB4


385.
LA28
LB4


386.
LA29
LB4


387.
LA30
LB4


388.
LA31
LB4


389.
LA32
LB4


390.
LA33
LB4


391.
LA34
LB4


392.
LA35
LB4


393.
LA36
LB4


394.
LA37
LB4


395.
LA38
LB4


396.
LA39
LB4


397.
LA40
LB4


398.
LA41
LB4


399.
LA42
LB4


400.
LA43
LB4


401.
LA44
LB4


402.
LA45
LB4


403.
LA46
LB4


404.
LA47
LB4


405.
LA48
LB4


406.
LA49
LB4


407.
LA50
LB4


408.
LA51
LB4


409.
LA52
LB4


410.
LA53
LB4


411.
LA54
LB4


412.
LA55
LB4


413.
LA56
LB4


414.
LA57
LB4


415.
LA58
LB4


416.
LA59
LB4


417.
LA60
LB4


418.
LA61
LB4


419.
LA62
LB4


420.
LA63
LB4


421.
LA64
LB4


422.
LA65
LB4


423.
LA66
LB4


424.
LA67
LB4


425.
LA68
LB4


426.
LA69
LB4


427.
LA70
LB4


428.
LA71
LB4


429.
LA72
LB4


430.
LA73
LB4


431.
LA74
LB4


432.
LA75
LB4


433.
LA76
LB4


434.
LA77
LB4


435.
LA78
LB4


436.
LA79
LB4


437.
LA80
LB4


438.
LA81
LB4


439.
LA82
LB4


440.
LA83
LB4


441.
LA84
LB4


442.
LA85
LB4


443.
LA86
LB4


444.
LA87
LB4


445.
LA88
LB4


446.
LA89
LB4


447.
LA90
LB4


448.
LA91
LB4


449.
LA92
LB4


450.
LA93
LB4


451.
LA94
LB4


452.
LA95
LB4


453.
LA96
LB4


454.
LA97
LB4


455.
LA98
LB4


456.
LA99
LB4


457.
LA100
LB4


458.
LA101
LB4


459.
LA102
LB4


460.
LA103
LB4


461.
LA104
LB4


462.
LA105
LB4


463.
LA106
LB4


464.
LA107
LB4


465.
LA108
LB4


466.
LA109
LB4


467.
LA110
LB4


468.
LA111
LB4


469.
LA112
LB4


470.
LA113
LB4


471.
LA114
LB4


472.
LA115
LB4


473.
LA116
LB4


474.
LA117
LB4


475.
LA118
LB4


476.
LA119
LB4


477.
LA1
LB5


478.
LA2
LB5


479.
LA3
LB5


480.
LA4
LB5


481.
LA5
LB5


482.
LA6
LB5


483.
LA7
LB5


484.
LA8
LB5


485.
LA9
LB5


486.
LA10
LB5


487.
LA11
LB5


488.
LA12
LB5


489.
LA13
LB5


490.
LA14
LB5


491.
LA15
LB5


492.
LA16
LB5


493.
LA17
LB5


494.
LA18
LB5


495.
LA19
LB5


496.
LA10
LB5


497.
LA21
LB5


498.
LA22
LB5


499.
LA23
LB5


500.
LA24
LB5


501.
LA25
LB5


502.
LA26
LB5


503.
LA27
LB5


504.
LA28
LB5


505.
LA29
LB5


506.
LA30
LB5


507.
LA31
LB5


508.
LA32
LB5


509.
LA33
LB5


510.
LA34
LB5


511.
LA35
LB5


512.
LA36
LB5


513.
LA37
LB5


514.
LA38
LB5


515.
LA39
LB5


516.
LA40
LB5


517.
LA41
LB5


518.
LA42
LB5


519.
LA43
LB5


520.
LA44
LB5


521.
LA45
LB5


522.
LA46
LB5


523.
LA47
LB5


524.
LA48
LB5


525.
LA49
LB5


526.
LA50
LB5


527.
LA51
LB5


528.
LA52
LB5


529.
LA53
LB5


530.
LA54
LB5


531.
LA55
LB5


532.
LA56
LB5


533.
LA57
LB5


534.
LA58
LB5


535.
LA59
LB5


536.
LA60
LB5


537.
LA61
LB5


538.
LA62
LB5


539.
LA63
LB5


540.
LA64
LB5


541.
LA65
LB5


542.
LA66
LB5


543.
LA67
LB5


544.
LA68
LB5


545.
LA69
LB5


546.
LA70
LB5


547.
LA71
LB5


548.
LA72
LB5


549.
LA73
LB5


550.
LA74
LB5


551.
LA75
LB5


552.
LA76
LB5


553.
LA77
LB5


554.
LA78
LB5


555.
LA79
LB5


556.
LA80
LB5


557.
LA81
LB5


558.
LA82
LB5


559.
LA83
LB5


560.
LA84
LB5


561.
LA85
LB5


562.
LA86
LB5


563.
LA87
LB5


564.
LA88
LB5


565.
LA89
LB5


566.
LA90
LB5


567.
LA91
LB5


568.
LA92
LB5


569.
LA93
LB5


570.
LA94
LB5


571.
LA95
LB5


572.
LA96
LB5


573.
LA97
LB5


574.
LA98
LB5


575.
LA99
LB5


576.
LA100
LB5


577.
LA101
LB5


578.
LA102
LB5


579.
LA103
LB5


580.
LA104
LB5


581.
LA105
LB5


582.
LA106
LB5


583.
LA107
LB5


584.
LA108
LB5


585.
LA109
LB5


586.
LA110
LB5


587.
LA111
LB5


588.
LA112
LB5


589.
LA113
LB5


590.
LA114
LB5


591.
LA115
LB5


592.
LA116
LB5


593.
LA117
LB5


594.
LA118
LB5


595.
LA119
LB5


596.
LA1
LB6


597.
LA2
LB6


598.
LA3
LB6


599.
LA4
LB6


600.
LA5
LB6


601.
LA6
LB6


602.
LA7
LB6


603.
LA8
LB6


604.
LA9
LB6


605.
LA10
LB6


606.
LA11
LB6


607.
LA12
LB6


608.
LA13
LB6


609.
LA14
LB6


610.
LA15
LB6


611.
LA16
LB6


612.
LA17
LB6


613.
LA18
LB6


614.
LA19
LB6


615.
LA10
LB6


616.
LA21
LB6


617.
LA22
LB6


618.
LA23
LB6


619.
LA24
LB6


620.
LA25
LB6


621.
LA26
LB6


622.
LA27
LB6


623.
LA28
LB6


624.
LA29
LB6


625.
LA30
LB6


626.
LA31
LB6


627.
LA32
LB6


628.
LA33
LB6


629.
LA34
LB6


630.
LA35
LB6


631.
LA36
LB6


632.
LA37
LB6


633.
LA38
LB6


634.
LA39
LB6


635.
LA40
LB6


636.
LA41
LB6


637.
LA42
LB6


638.
LA43
LB6


639.
LA44
LB6


640.
LA45
LB6


641.
LA46
LB6


642.
LA47
LB6


643.
LA48
LB6


644.
LA49
LB6


645.
LA50
LB6


646.
LA51
LB6


647.
LA52
LB6


648.
LA53
LB6


649.
LA54
LB6


650.
LA55
LB6


651.
LA56
LB6


652.
LA57
LB6


653.
LA58
LB6


654.
LA59
LB6


655.
LA60
LB6


656.
LA61
LB6


657.
LA62
LB6


658.
LA63
LB6


659.
LA64
LB6


660.
LA65
LB6


661.
LA66
LB6


662.
LA67
LB6


663.
LA68
LB6


664.
LA69
LB6


665.
LA70
LB6


666.
LA71
LB6


667.
LA72
LB6


668.
LA73
LB6


669.
LA74
LB6


670.
LA75
LB6


671.
LA76
LB6


672.
LA77
LB6


673.
LA78
LB6


674.
LA79
LB6


675.
LA80
LB6


676.
LA81
LB6


677.
LA82
LB6


678.
LA83
LB6


679.
LA84
LB6


680.
LA85
LB6


681.
LA86
LB6


682.
LA87
LB6


683.
LA88
LB6


684.
LA89
LB6


685.
LA90
LB6


686.
LA91
LB6


687.
LA92
LB6


688.
LA93
LB6


689.
LA94
LB6


690.
LA95
LB6


691.
LA96
LB6


692.
LA97
LB6


693.
LA98
LB6


694.
LA99
LB6


695.
LA100
LB6


696.
LA101
LB6


697.
LA102
LB6


698.
LA103
LB6


699.
LA104
LB6


700.
LA105
LB6


701.
LA106
LB6


702.
LA107
LB6


703.
LA108
LB6


704.
LA109
LB6


705.
LA110
LB6


706.
LA111
LB6


707.
LA112
LB6


708.
LA113
LB6


709.
LA114
LB6


710.
LA115
LB6


711.
LA116
LB6


712.
LA117
LB6


713.
LA118
LB6


714.
LA119
LB6


715.
LA1
LB7


716.
LA2
LB7


717.
LA3
LB7


718.
LA4
LB7


719.
LA5
LB7


720.
LA6
LB7


721.
LA7
LB7


722.
LA8
LB7


723.
LA9
LB7


724.
LA10
LB7


725.
LA11
LB7


726.
LA12
LB7


727.
LA13
LB7


728.
LA14
LB7


729.
LA15
LB7


730.
LA16
LB7


731.
LA17
LB7


732.
LA18
LB7


733.
LA19
LB7


734.
LA10
LB7


735.
LA21
LB7


736.
LA22
LB7


737.
LA23
LB7


738.
LA24
LB7


739.
LA25
LB7


740.
LA26
LB7


741.
LA27
LB7


742.
LA28
LB7


743.
LA29
LB7


744.
LA30
LB7


745.
LA31
LB7


746.
LA32
LB7


747.
LA33
LB7


748.
LA34
LB7


749.
LA35
LB7


750.
LA36
LB7


751.
LA37
LB7


752.
LA38
LB7


753.
LA39
LB7


754.
LA40
LB7


755.
LA41
LB7


756.
LA42
LB7


757.
LA43
LB7


758.
LA44
LB7


759.
LA45
LB7


760.
LA46
LB7


761.
LA47
LB7


762.
LA48
LB7


763.
LA49
LB7


764.
LA50
LB7


765.
LA51
LB7


766.
LA52
LB7


767.
LA53
LB7


768.
LA54
LB7


769.
LA55
LB7


770.
LA56
LB7


771.
LA57
LB7


772.
LA58
LB7


773.
LA59
LB7


774.
LA60
LB7


775.
LA61
LB7


776.
LA62
LB7


777.
LA63
LB7


778.
LA64
LB7


779.
LA65
LB7


780.
LA66
LB7


781.
LA67
LB7


782.
LA68
LB7


783.
LA69
LB7


784.
LA70
LB7


785.
LA71
LB7


786.
LA72
LB7


787.
LA73
LB7


788.
LA74
LB7


789.
LA75
LB7


790.
LA76
LB7


791.
LA77
LB7


792.
LA78
LB7


793.
LA79
LB7


794.
LA80
LB7


795.
LA81
LB7


796.
LA82
LB7


797.
LA83
LB7


798.
LA84
LB7


799.
LA85
LB7


800.
LA86
LB7


801.
LA87
LB7


802.
LA88
LB7


803.
LA89
LB7


804.
LA90
LB7


805.
LA91
LB7


806.
LA92
LB7


807.
LA93
LB7


808.
LA94
LB7


809.
LA95
LB7


810.
LA96
LB7


811.
LA97
LB7


812.
LA98
LB7


813.
LA99
LB7


814.
LA100
LB7


815.
LA101
LB7


816.
LA102
LB7


817.
LA103
LB7


818.
LA104
LB7


819.
LA105
LB7


820.
LA106
LB7


821.
LA107
LB7


822.
LA108
LB7


823.
LA109
LB7


824.
LA110
LB7


825.
LA111
LB7


826.
LA112
LB7


827.
LA113
LB7


828.
LA114
LB7


829.
LA115
LB7


830.
LA116
LB7


831.
LA117
LB7


832.
LA118
LB7


833.
LA119
LB7


834.
LA1
LB8


835.
LA2
LB8


836.
LA3
LB8


837.
LA4
LB8


838.
LA5
LB8


839.
LA6
LB8


840.
LA7
LB8


841.
LA8
LB8


842.
LA9
LB8


843.
LA10
LB8


844.
LA11
LB8


845.
LA12
LB8


846.
LA13
LB8


847.
LA14
LB8


848.
LA15
LB8


849.
LA16
LB8


850.
LA17
LB8


851.
LA18
LB8


852.
LA19
LB8


853.
LA10
LB8


854.
LA21
LB8


855.
LA22
LB8


856.
LA23
LB8


857.
LA24
LB8


858.
LA25
LB8


859.
LA26
LB8


860.
LA27
LB8


861.
LA28
LB8


862.
LA29
LB8


863.
LA30
LB8


864.
LA31
LB8


865.
LA32
LB8


866.
LA33
LB8


867.
LA34
LB8


868.
LA35
LB8


869.
LA36
LB8


870.
LA37
LB8


871.
LA38
LB8


872.
LA39
LB8


873.
LA40
LB8


874.
LA41
LB8


875.
LA42
LB8


876.
LA43
LB8


877.
LA44
LB8


878.
LA45
LB8


879.
LA46
LB8


880.
LA47
LB8


881.
LA48
LB8


882.
LA49
LB8


883.
LA50
LB8


884.
LA51
LB8


885.
LA52
LB8


886.
LA53
LB8


887.
LA54
LB8


888.
LA55
LB8


889.
LA56
LB8


890.
LA57
LB8


891.
LA58
LB8


892.
LA59
LB8


893.
LA60
LB8


894.
LA61
LB8


895.
LA62
LB8


896.
LA63
LB8


897.
LA64
LB8


898.
LA65
LB8


899.
LA66
LB8


900.
LA67
LB8


901.
LA68
LB8


902.
LA69
LB8


903.
LA70
LB8


904.
LA71
LB8


905.
LA72
LB8


906.
LA73
LB8


907.
LA74
LB8


908.
LA75
LB8


909.
LA76
LB8


910.
LA77
LB8


911.
LA78
LB8


912.
LA79
LB8


913.
LA80
LB8


914.
LA81
LB8


915.
LA82
LB8


916.
LA83
LB8


917.
LA84
LB8


918.
LA85
LB8


919.
LA86
LB8


920.
LA87
LB8


921.
LA88
LB8


922.
LA89
LB8


923.
LA90
LB8


924.
LA91
LB8


925.
LA92
LB8


926.
LA93
LB8


927.
LA94
LB8


928.
LA95
LB8


929.
LA96
LB8


930.
LA97
LB8


931.
LA98
LB8


932.
LA99
LB8


933.
LA100
LB8


934.
LA101
LB8


935.
LA102
LB8


936.
LA103
LB8


937.
LA104
LB8


938.
LA105
LB8


939.
LA106
LB8


940.
LA107
LB8


941.
LA108
LB8


942.
LA109
LB8


943.
LA110
LB8


944.
LA111
LB8


945.
LA112
LB8


946.
LA113
LB8


947.
LA114
LB8


948.
LA115
LB8


949.
LA116
LB8


950.
LA117
LB8


951.
LA118
LB8


952.
LA119
LB8


953.
LA1
LB9


954.
LA2
LB9


955.
LA3
LB9


956.
LA4
LB9


957.
LA5
LB9


958.
LA6
LB9


959.
LA7
LB9


960.
LA8
LB9


961.
LA9
LB9


962.
LA10
LB9


963.
LA11
LB9


964.
LA12
LB9


965.
LA13
LB9


966.
LA14
LB9


967.
LA15
LB9


968.
LA16
LB9


969.
LA17
LB9


970.
LA18
LB9


971.
LA19
LB9


972.
LA10
LB9


973.
LA21
LB9


974.
LA22
LB9


975.
LA23
LB9


976.
LA24
LB9


977.
LA25
LB9


978.
LA26
LB9


979.
LA27
LB9


980.
LA28
LB9


981.
LA29
LB9


982.
LA30
LB9


983.
LA31
LB9


984.
LA32
LB9


985.
LA33
LB9


986.
LA34
LB9


987.
LA35
LB9


988.
LA36
LB9


989.
LA37
LB9


990.
LA38
LB9


991.
LA39
LB9


992.
LA40
LB9


993.
LA41
LB9


994.
LA42
LB9


995.
LA43
LB9


996.
LA44
LB9


997.
LA45
LB9


998.
LA46
LB9


999.
LA47
LB9


1000.
LA48
LB9


1001.
LA49
LB9


1002.
LA50
LB9


1003.
LA51
LB9


1004.
LA52
LB9


1005.
LA53
LB9


1006.
LA54
LB9


1007.
LA55
LB9


1008.
LA56
LB9


1009.
LA57
LB9


1010.
LA58
LB9


1011.
LA59
LB9


1012.
LA60
LB9


1013.
LA61
LB9


1014.
LA62
LB9


1015.
LA63
LB9


1016.
LA64
LB9


1017.
LA65
LB9


1018.
LA66
LB9


1019.
LA67
LB9


1020.
LA68
LB9


1021.
LA69
LB9


1022.
LA70
LB9


1023.
LA71
LB9


1024.
LA72
LB9


1025.
LA73
LB9


1026.
LA74
LB9


1027.
LA75
LB9


1028.
LA76
LB9


1029.
LA77
LB9


1030.
LA78
LB9


1031.
LA79
LB9


1032.
LA80
LB9


1033.
LA81
LB9


1034.
LA82
LB9


1035.
LA83
LB9


1036.
LA84
LB9


1037.
LA85
LB9


1038.
LA86
LB9


1039.
LA87
LB9


1040.
LA88
LB9


1041.
LA89
LB9


1042.
LA90
LB9


1043.
LA91
LB9


1044.
LA92
LB9


1045.
LA93
LB9


1046.
LA94
LB9


1047.
LA95
LB9


1048.
LA96
LB9


1049.
LA97
LB9


1050.
LA98
LB9


1051.
LA99
LB9


1052.
LA100
LB9


1053.
LA101
LB9


1054.
LA102
LB9


1055.
LA103
LB9


1056.
LA104
LB9


1057.
LA105
LB9


1058.
LA106
LB9


1059.
LA107
LB9


1060.
LA108
LB9


1061.
LA109
LB9


1062.
LA110
LB9


1063.
LA111
LB9


1064.
LA112
LB9


1065.
LA113
LB9


1066.
LA114
LB9


1067.
LA115
LB9


1068.
LA116
LB9


1069.
LA117
LB9


1070.
LA118
LB9


1071.
LA119
LB9


1072.
LA1
LB10


1073.
LA2
LB10


1074.
LA3
LB10


1075.
LA4
LB10


1076.
LA5
LB10


1077.
LA6
LB10


1078.
LA7
LB10


1079.
LA8
LB10


1080.
LA9
LB10


1081.
LA10
LB10


1082.
LA11
LB10


1083.
LA12
LB10


1084.
LA13
LB10


1085.
LA14
LB10


1086.
LA15
LB10


1087.
LA16
LB10


1088.
LA17
LB10


1089.
LA18
LB10


1090.
LA19
LB10


1091.
LA10
LB10


1092.
LA21
LB10


1093.
LA22
LB10


1094.
LA23
LB10


1095.
LA24
LB10


1096.
LA25
LB10


1097.
LA26
LB10


1098.
LA27
LB10


1099.
LA28
LB10


1100.
LA29
LB10


1101.
LA30
LB10


1102.
LA31
LB10


1103.
LA32
LB10


1104.
LA33
LB10


1105.
LA34
LB10


1106.
LA35
LB10


1107.
LA36
LB10


1108.
LA37
LB10


1109.
LA38
LB10


1110.
LA39
LB10


1111.
LA40
LB10


1112.
LA41
LB10


1113.
LA42
LB10


1114.
LA43
LB10


1115.
LA44
LB10


1116.
LA45
LB10


1117.
LA46
LB10


1118.
LA47
LB10


1119.
LA48
LB10


1120.
LA49
LB10


1121.
LA50
LB10


1122.
LA51
LB10


1123.
LA52
LB10


1124.
LA53
LB10


1125.
LA54
LB10


1126.
LA55
LB10


1127.
LA56
LB10


1128.
LA57
LB10


1129.
LA58
LB10


1130.
LA59
LB10


1131.
LA60
LB10


1132.
LA61
LB10


1133.
LA62
LB10


1134.
LA63
LB10


1135.
LA64
LB10


1136.
LA65
LB10


1137.
LA66
LB10


1138.
LA67
LB10


1139.
LA68
LB10


1140.
LA69
LB10


1141.
LA70
LB10


1142.
LA71
LB10


1143.
LA72
LB10


1144.
LA73
LB10


1145.
LA74
LB10


1146.
LA75
LB10


1147.
LA76
LB10


1148.
LA77
LB10


1149.
LA78
LB10


1150.
LA79
LB10


1151.
LA80
LB10


1152.
LA81
LB10


1153.
LA82
LB10


1154.
LA83
LB10


1155.
LA84
LB10


1156.
LA85
LB10


1157.
LA86
LB10


1158.
LA87
LB10


1159.
LA88
LB10


1160.
LA89
LB10


1161.
LA90
LB10


1162.
LA91
LB10


1163.
LA92
LB10


1164.
LA93
LB10


1165.
LA94
LB10


1166.
LA95
LB10


1167.
LA96
LB10


1168.
LA97
LB10


1169.
LA98
LB10


1170.
LA99
LB10


1171.
LA100
LB10


1172.
LA101
LB10


1173.
LA102
LB10


1174.
LA103
LB10


1175.
LA104
LB10


1176.
LA105
LB10


1177.
LA106
LB10


1178.
LA107
LB10


1179.
LA108
LB10


1180.
LA109
LB10


1181.
LA110
LB10


1182.
LA111
LB10


1183.
LA112
LB10


1184.
LA113
LB10


1185.
LA114
LB10


1186.
LA115
LB10


1187.
LA116
LB10


1188.
LA117
LB10


1189.
LA118
LB10


1190.
LA119
LB10


1191.
LA1
LB11


1192.
LA2
LB11


1193.
LA3
LB11


1194.
LA4
LB11


1195.
LA5
LB11


1196.
LA6
LB11


1197.
LA7
LB11


1198.
LA8
LB11


1199.
LA9
LB11


1200.
LA10
LB11


1201.
LA11
LB11


1202.
LA12
LB11


1203.
LA13
LB11


1204.
LA14
LB11


1205.
LA15
LB11


1206.
LA16
LB11


1207.
LA17
LB11


1208.
LA18
LB11


1209.
LA19
LB11


1210.
LA10
LB11


1211.
LA21
LB11


1212.
LA22
LB11


1213.
LA23
LB11


1214.
LA24
LB11


1215.
LA25
LB11


1216.
LA26
LB11


1217.
LA27
LB11


1218.
LA28
LB11


1219.
LA29
LB11


1220.
LA30
LB11


1221.
LA31
LB11


1222.
LA32
LB11


1223.
LA33
LB11


1224.
LA34
LB11


1225.
LA35
LB11


1226.
LA36
LB11


1227.
LA37
LB11


1228.
LA38
LB11


1229.
LA39
LB11


1230.
LA40
LB11


1231.
LA41
LB11


1232.
LA42
LB11


1233.
LA43
LB11


1234.
LA44
LB11


1235.
LA45
LB11


1236.
LA46
LB11


1237.
LA47
LB11


1238.
LA48
LB11


1239.
LA49
LB11


1240.
LA50
LB11


1241.
LA51
LB11


1242.
LA52
LB11


1243.
LA53
LB11


1244.
LA54
LB11


1245.
LA55
LB11


1246.
LA56
LB11


1247.
LA57
LB11


1248.
LA58
LB11


1249.
LA59
LB11


1250.
LA60
LB11


1251.
LA61
LB11


1252.
LA62
LB11


1253.
LA63
LB11


1254.
LA64
LB11


1255.
LA65
LB11


1256.
LA66
LB11


1257.
LA67
LB11


1258.
LA68
LB11


1259.
LA69
LB11


1260.
LA70
LB11


1261.
LA71
LB11


1262.
LA72
LB11


1263.
LA73
LB11


1264.
LA74
LB11


1265.
LA75
LB11


1266.
LA76
LB11


1267.
LA77
LB11


1268.
LA78
LB11


1269.
LA79
LB11


1270.
LA80
LB11


1271.
LA81
LB11


1272.
LA82
LB11


1273.
LA83
LB11


1274.
LA84
LB11


1275.
LA85
LB11


1276.
LA86
LB11


1277.
LA87
LB11


1278.
LA88
LB11


1279.
LA89
LB11


1280.
LA90
LB11


1281.
LA91
LB11


1282.
LA92
LB11


1283.
LA93
LB11


1284.
LA94
LB11


1285.
LA95
LB11


1286.
LA96
LB11


1287.
LA97
LB11


1288.
LA98
LB11


1289.
LA99
LB11


1290.
LA100
LB11


1291.
LA101
LB11


1292.
LA102
LB11


1293.
LA103
LB11


1294.
LA104
LB11


1295.
LA105
LB11


1296.
LA106
LB11


1297.
LA107
LB11


1298.
LA108
LB11


1299.
LA109
LB11


1300.
LA110
LB11


1301.
LA111
LB11


1302.
LA112
LB11


1303.
LA113
LB11


1304.
LA114
LB11


1305.
LA115
LB11


1306.
LA116
LB11


1307.
LA117
LB11


1308.
LA118
LB11


1309.
LA119
LB11


1310.
LA1
LB12


1311.
LA2
LB12


1312.
LA3
LB12


1313.
LA4
LB12


1314.
LA5
LB12


1315.
LA6
LB12


1316.
LA7
LB12


1317.
LA8
LB12


1318.
LA9
LB12


1319.
LA10
LB12


1320.
LA11
LB12


1321.
LA12
LB12


1322.
LA13
LB12


1323.
LA14
LB12


1324.
LA15
LB12


1325.
LA16
LB12


1326.
LA17
LB12


1327.
LA18
LB12


1328.
LA19
LB12


1329.
LA10
LB12


1330.
LA21
LB12


1331.
LA22
LB12


1332.
LA23
LB12


1333.
LA24
LB12


1334.
LA25
LB12


1335.
LA26
LB12


1336.
LA27
LB12


1337.
LA28
LB12


1338.
LA29
LB12


1339.
LA30
LB12


1340.
LA31
LB12


1341.
LA32
LB12


1342.
LA33
LB12


1343.
LA34
LB12


1344.
LA35
LB12


1345.
LA36
LB12


1346.
LA37
LB12


1347.
LA38
LB12


1348.
LA39
LB12


1349.
LA40
LB12


1350.
LA41
LB12


1351.
LA42
LB12


1352.
LA43
LB12


1353.
LA44
LB12


1354.
LA45
LB12


1355.
LA46
LB12


1356.
LA47
LB12


1357.
LA48
LB12


1358.
LA49
LB12


1359.
LA50
LB12


1360.
LA51
LB12


1361.
LA52
LB12


1362.
LA53
LB12


1363.
LA54
LB12


1364.
LA55
LB12


1365.
LA56
LB12


1366.
LA57
LB12


1367.
LA58
LB12


1368.
LA59
LB12


1369.
LA60
LB12


1370.
LA61
LB12


1371.
LA62
LB12


1372.
LA63
LB12


1373.
LA64
LB12


1374.
LA65
LB12


1375.
LA66
LB12


1376.
LA67
LB12


1377.
LA68
LB12


1378.
LA69
LB12


1379.
LA70
LB12


1380.
LA71
LB12


1381.
LA72
LB12


1382.
LA73
LB12


1383.
LA74
LB12


1384.
LA75
LB12


1385.
LA76
LB12


1386.
LA77
LB12


1387.
LA78
LB12


1388.
LA79
LB12


1389.
LA80
LB12


1390.
LA81
LB12


1391.
LA82
LB12


1392.
LA83
LB12


1393.
LA84
LB12


1394.
LA85
LB12


1395.
LA86
LB12


1396.
LA87
LB12


1397.
LA88
LB12


1398.
LA89
LB12


1399.
LA90
LB12


1400.
LA91
LB12


1401.
LA92
LB12


1402.
LA93
LB12


1403.
LA94
LB12


1404.
LA95
LB12


1405.
LA96
LB12


1406.
LA97
LB12


1407.
LA98
LB12


1408.
LA99
LB12


1409.
LA100
LB12


1410.
LA101
LB12


1411.
LA102
LB12


1412.
LA103
LB12


1413.
LA104
LB12


1414.
LA105
LB12


1415.
LA106
LB12


1416.
LA107
LB12


1417.
LA108
LB12


1418.
LA109
LB12


1419.
LA110
LB12


1420.
LA111
LB12


1421.
LA112
LB12


1422.
LA113
LB12


1423.
LA114
LB12


1424.
LA115
LB12


1425.
LA116
LB12


1426.
LA117
LB12


1427.
LA118
LB12


1428.
LA119
LB12


1429.
LA1
LB13


1430.
LA2
LB13


1431.
LA3
LB13


1432.
LA4
LB13


1433.
LA5
LB13


1434.
LA6
LB13


1435.
LA7
LB13


1436.
LA8
LB13


1437.
LA9
LB13


1438.
LA10
LB13


1439.
LA11
LB13


1440.
LA12
LB13


1441.
LA13
LB13


1442.
LA14
LB13


1443.
LA15
LB13


1444.
LA16
LB13


1445.
LA17
LB13


1446.
LA18
LB13


1447.
LA19
LB13


1448.
LA10
LB13


1449.
LA21
LB13


1450.
LA22
LB13


1451.
LA23
LB13


1452.
LA24
LB13


1453.
LA25
LB13


1454.
LA26
LB13


1455.
LA27
LB13


1456.
LA28
LB13


1457.
LA29
LB13


1458.
LA30
LB13


1459.
LA31
LB13


1460.
LA32
LB13


1461.
LA33
LB13


1462.
LA34
LB13


1463.
LA35
LB13


1464.
LA36
LB13


1465.
LA37
LB13


1466.
LA38
LB13


1467.
LA39
LB13


1468.
LA40
LB13


1469.
LA41
LB13


1470.
LA42
LB13


1471.
LA43
LB13


1472.
LA44
LB13


1473.
LA45
LB13


1474.
LA46
LB13


1475.
LA47
LB13


1476.
LA48
LB13


1477.
LA49
LB13


1478.
LA50
LB13


1479.
LA51
LB13


1480.
LA52
LB13


1481.
LA53
LB13


1482.
LA54
LB13


1483.
LA55
LB13


1484.
LA56
LB13


1485.
LA57
LB13


1486.
LA58
LB13


1487.
LA59
LB13


1488.
LA60
LB13


1489.
LA61
LB13


1490.
LA62
LB13


1491.
LA63
LB13


1492.
LA64
LB13


1493.
LA65
LB13


1494.
LA66
LB13


1495.
LA67
LB13


1496.
LA68
LB13


1497.
LA69
LB13


1498.
LA70
LB13


1499.
LA71
LB13


1500.
LA72
LB13


1501.
LA73
LB13


1502.
LA74
LB13


1503.
LA75
LB13


1504.
LA76
LB13


1505.
LA77
LB13


1506.
LA78
LB13


1507.
LA79
LB13


1508.
LA80
LB13


1509.
LA81
LB13


1510.
LA82
LB13


1511.
LA83
LB13


1512.
LA84
LB13


1513.
LA85
LB13


1514.
LA86
LB13


1515.
LA87
LB13


1516.
LA88
LB13


1517.
LA89
LB13


1518.
LA90
LB13


1519.
LA91
LB13


1520.
LA92
LB13


1521.
LA93
LB13


1522.
LA94
LB13


1523.
LA95
LB13


1524.
LA96
LB13


1525.
LA97
LB13


1526.
LA98
LB13


1527.
LA99
LB13


1528.
LA100
LB13


1529.
LA101
LB13


1530.
LA102
LB13


1531.
LA103
LB13


1532.
LA104
LB13


1533.
LA105
LB13


1534.
LA106
LB13


1535.
LA107
LB13


1536.
LA108
LB13


1537.
LA109
LB13


1538.
LA110
LB13


1539.
LA111
LB13


1540.
LA112
LB13


1541.
LA113
LB13


1542.
LA114
LB13


1543.
LA115
LB13


1544.
LA116
LB13


1545.
LA117
LB13


1546.
LA118
LB13


1547.
LA119
LB13


1548.
LA1
LB14


1549.
LA2
LB14


1550.
LA3
LB14


1551.
LA4
LB14


1552.
LA5
LB14


1553.
LA6
LB14


1554.
LA7
LB14


1555.
LA8
LB14


1556.
LA9
LB14


1557.
LA10
LB14


1558.
LA11
LB14


1559.
LA12
LB14


1560.
LA13
LB14


1561.
LA14
LB14


1562.
LA15
LB14


1563.
LA16
LB14


1564.
LA17
LB14


1565.
LA18
LB14


1566.
LA19
LB14


1567.
LA10
LB14


1568.
LA21
LB14


1569.
LA22
LB14


1570.
LA23
LB14


1571.
LA24
LB14


1572.
LA25
LB14


1573.
LA26
LB14


1574.
LA27
LB14


1575.
LA28
LB14


1576.
LA29
LB14


1577.
LA30
LB14


1578.
LA31
LB14


1579.
LA32
LB14


1580.
LA33
LB14


1581.
LA34
LB14


1582.
LA35
LB14


1583.
LA36
LB14


1584.
LA37
LB14


1585.
LA38
LB14


1586.
LA39
LB14


1587.
LA40
LB14


1588.
LA41
LB14


1589.
LA42
LB14


1590.
LA43
LB14


1591.
LA44
LB14


1592.
LA45
LB14


1593.
LA46
LB14


1594.
LA47
LB14


1595.
LA48
LB14


1596.
LA49
LB14


1597.
LA50
LB14


1598.
LA51
LB14


1599.
LA52
LB14


1600.
LA53
LB14


1601.
LA54
LB14


1602.
LA55
LB14


1603.
LA56
LB14


1604.
LA57
LB14


1605.
LA58
LB14


1606.
LA59
LB14


1607.
LA60
LB14


1608.
LA61
LB14


1609.
LA62
LB14


1610.
LA63
LB14


1611.
LA64
LB14


1612.
LA65
LB14


1613.
LA66
LB14


1614.
LA67
LB14


1615.
LA68
LB14


1616.
LA69
LB14


1617.
LA70
LB14


1618.
LA71
LB14


1619.
LA72
LB14


1620.
LA73
LB14


1621.
LA74
LB14


1622.
LA75
LB14


1623.
LA76
LB14


1624.
LA77
LB14


1625.
LA78
LB14


1626.
LA79
LB14


1627.
LA80
LB14


1628.
LA81
LB14


1629.
LA82
LB14


1630.
LA83
LB14


1631.
LA84
LB14


1632.
LA85
LB14


1633.
LA86
LB14


1634.
LA87
LB14


1635.
LA88
LB14


1636.
LA89
LB14


1637.
LA90
LB14


1638.
LA91
LB14


1639.
LA92
LB14


1640.
LA93
LB14


1641.
LA94
LB14


1642.
LA95
LB14


1643.
LA96
LB14


1644.
LA97
LB14


1645.
LA98
LB14


1646.
LA99
LB14


1647.
LA100
LB14


1648.
LA101
LB14


1649.
LA102
LB14


1650.
LA103
LB14


1651.
LA104
LB14


1652.
LA105
LB14


1653.
LA106
LB14


1654.
LA107
LB14


1655.
LA108
LB14


1656.
LA109
LB14


1657.
LA110
LB14


1658.
LA111
LB14


1659.
LA112
LB14


1660.
LA113
LB14


1661.
LA114
LB14


1662.
LA115
LB14


1663.
LA116
LB14


1664.
LA117
LB14


1665.
LA118
LB14


1666.
LA119
LB14


1667.
LA1
LB15


1668.
LA2
LB15


1669.
LA3
LB15


1670.
LA4
LB15


1671.
LA5
LB15


1672.
LA6
LB15


1673.
LA7
LB15


1674.
LA8
LB15


1675.
LA9
LB15


1676.
LA10
LB15


1677.
LA11
LB15


1678.
LA12
LB15


1679.
LA13
LB15


1680.
LA14
LB15


1681.
LA15
LB15


1682.
LA16
LB15


1683.
LA17
LB15


1684.
LA18
LB15


1685.
LA19
LB15


1686.
LA10
LB15


1687.
LA21
LB15


1688.
LA22
LB15


1689.
LA23
LB15


1690.
LA24
LB15


1691.
LA25
LB15


1692.
LA26
LB15


1693.
LA27
LB15


1694.
LA28
LB15


1695.
LA29
LB15


1696.
LA30
LB15


1697.
LA31
LB15


1698.
LA32
LB15


1699.
LA33
LB15


1700.
LA34
LB15


1701.
LA35
LB15


1702.
LA36
LB15


1703.
LA37
LB15


1704.
LA38
LB15


1705.
LA39
LB15


1706.
LA40
LB15


1707.
LA41
LB15


1708.
LA42
LB15


1709.
LA43
LB15


1710.
LA44
LB15


1711.
LA45
LB15


1712.
LA46
LB15


1713.
LA47
LB15


1714.
LA48
LB15


1715.
LA49
LB15


1716.
LA50
LB15


1717.
LA51
LB15


1718.
LA52
LB15


1719.
LA53
LB15


1720.
LA54
LB15


1721.
LA55
LB15


1722.
LA56
LB15


1723.
LA57
LB15


1724.
LA58
LB15


1725.
LA59
LB15


1726.
LA60
LB15


1727.
LA61
LB15


1728.
LA62
LB15


1729.
LA63
LB15


1730.
LA64
LB15


1731.
LA65
LB15


1732.
LA66
LB15


1733.
LA67
LB15


1734.
LA68
LB15


1735.
LA69
LB15


1736.
LA70
LB15


1737.
LA71
LB15


1738.
LA72
LB15


1739.
LA73
LB15


1740.
LA74
LB15


1741.
LA75
LB15


1742.
LA76
LB15


1743.
LA77
LB15


1744.
LA78
LB15


1745.
LA79
LB15


1746.
LA80
LB15


1747.
LA81
LB15


1748.
LA82
LB15


1749.
LA83
LB15


1750.
LA84
LB15


1751.
LA85
LB15


1752.
LA86
LB15


1753.
LA87
LB15


1754.
LA88
LB15


1755.
LA89
LB15


1756.
LA90
LB15


1757.
LA91
LB15


1758.
LA92
LB15


1759.
LA93
LB15


1760.
LA94
LB15


1761.
LA95
LB15


1762.
LA96
LB15


1763.
LA97
LB15


1764.
LA98
LB15


1765.
LA99
LB15


1766.
LA100
LB15


1767.
LA101
LB15


1768.
LA102
LB15


1769.
LA103
LB15


1770.
LA104
LB15


1771.
LA105
LB15


1772.
LA106
LB15


1773.
LA107
LB15


1774.
LA108
LB15


1775.
LA109
LB15


1776.
LA110
LB15


1777.
LA111
LB15


1778.
LA112
LB15


1779.
LA113
LB15


1780.
LA114
LB15


1781.
LA115
LB15


1782.
LA116
LB15


1783.
LA117
LB15


1784.
LA118
LB15


1785.
LA119
LB15


1786.
LA1
LB16


1787.
LA2
LB16


1788.
LA3
LB16


1789.
LA4
LB16


1790.
LA5
LB16


1791.
LA6
LB16


1792.
LA7
LB16


1793.
LA8
LB16


1794.
LA9
LB16


1795.
LA10
LB16


1796.
LA11
LB16


1797.
LA12
LB16


1798.
LA13
LB16


1799.
LA14
LB16


1800.
LA15
LB16


1801.
LA16
LB16


1802.
LA17
LB16


1803.
LA18
LB16


1804.
LA19
LB16


1805.
LA10
LB16


1806.
LA21
LB16


1807.
LA22
LB16


1808.
LA23
LB16


1809.
LA24
LB16


1810.
LA25
LB16


1811.
LA26
LB16


1812.
LA27
LB16


1813.
LA28
LB16


1814.
LA29
LB16


1815.
LA30
LB16


1816.
LA31
LB16


1817.
LA32
LB16


1818.
LA33
LB16


1819.
LA34
LB16


1820.
LA35
LB16


1821.
LA36
LB16


1822.
LA37
LB16


1823.
LA38
LB16


1824.
LA39
LB16


1825.
LA40
LB16


1826.
LA41
LB16


1827.
LA42
LB16


1828.
LA43
LB16


1829.
LA44
LB16


1830.
LA45
LB16


1831.
LA46
LB16


1832.
LA47
LB16


1833.
LA48
LB16


1834.
LA49
LB16


1835.
LA50
LB16


1836.
LA51
LB16


1837.
LA52
LB16


1838.
LA53
LB16


1839.
LA54
LB16


1840.
LA55
LB16


1841.
LA56
LB16


1842.
LA57
LB16


1843.
LA58
LB16


1844.
LA59
LB16


1845.
LA60
LB16


1846.
LA61
LB16


1847.
LA62
LB16


1848.
LA63
LB16


1849.
LA64
LB16


1850.
LA65
LB16


1851.
LA66
LB16


1852.
LA67
LB16


1853.
LA68
LB16


1854.
LA69
LB16


1855.
LA70
LB16


1856.
LA71
LB16


1857.
LA72
LB16


1858.
LA73
LB16


1859.
LA74
LB16


1860.
LA75
LB16


1861.
LA76
LB16


1862.
LA77
LB16


1863.
LA78
LB16


1864.
LA79
LB16


1865.
LA80
LB16


1866.
LA81
LB16


1867.
LA82
LB16


1868.
LA83
LB16


1869.
LA84
LB16


1870.
LA85
LB16


1871.
LA86
LB16


1872.
LA87
LB16


1873.
LA88
LB16


1874.
LA89
LB16


1875.
LA90
LB16


1876.
LA91
LB16


1877.
LA92
LB16


1878.
LA93
LB16


1879.
LA94
LB16


1880.
LA95
LB16


1881.
LA96
LB16


1882.
LA97
LB16


1883.
LA98
LB16


1884.
LA99
LB16


1885.
LA100
LB16


1886.
LA101
LB16


1887.
LA102
LB16


1888.
LA103
LB16


1889.
LA104
LB16


1890.
LA105
LB16


1891.
LA106
LB16


1892.
LA107
LB16


1893.
LA108
LB16


1894.
LA109
LB16


1895.
LA110
LB16


1896.
LA111
LB16


1897.
LA112
LB16


1898.
LA113
LB16


1899.
LA114
LB16


1900.
LA115
LB16


1901.
LA116
LB16


1902.
LA117
LB16


1903.
LA118
LB16


1904.
LA119
LB16


1905.
LA1
LB17


1906.
LA2
LB17


1907.
LA3
LB17


1908.
LA4
LB17


1909.
LA5
LB17


1910.
LA6
LB17


1911.
LA7
LB17


1912.
LA8
LB17


1913.
LA9
LB17


1914.
LA10
LB17


1915.
LA11
LB17


1916.
LA12
LB17


1917.
LA13
LB17


1918.
LA14
LB17


1919.
LA15
LB17


1920.
LA16
LB17


1921.
LA17
LB17


1922.
LA18
LB17


1923.
LA19
LB17


1924.
LA10
LB17


1925.
LA21
LB17


1926.
LA22
LB17


1927.
LA23
LB17


1928.
LA24
LB17


1929.
LA25
LB17


1930.
LA26
LB17


1931.
LA27
LB17


1932.
LA28
LB17


1933.
LA29
LB17


1934.
LA30
LB17


1935.
LA31
LB17


1936.
LA32
LB17


1937.
LA33
LB17


1938.
LA34
LB17


1939.
LA35
LB17


1940.
LA36
LB17


1941.
LA37
LB17


1942.
LA38
LB17


1943.
LA39
LB17


1944.
LA40
LB17


1945.
LA41
LB17


1946.
LA42
LB17


1947.
LA43
LB17


1948.
LA44
LB17


1949.
LA45
LB17


1950.
LA46
LB17


1951.
LA47
LB17


1952.
LA48
LB17


1953.
LA49
LB17


1954.
LA50
LB17


1955.
LA51
LB17


1956.
LA52
LB17


1957.
LA53
LB17


1958.
LA54
LB17


1959.
LA55
LB17


1960.
LA56
LB17


1961.
LA57
LB17


1962.
LA58
LB17


1963.
LA59
LB17


1964.
LA60
LB17


1965.
LA61
LB17


1966.
LA62
LB17


1967.
LA63
LB17


1968.
LA64
LB17


1969.
LA65
LB17


1970.
LA66
LB17


1971.
LA67
LB17


1972.
LA68
LB17


1973.
LA69
LB17


1974.
LA70
LB17


1975.
LA71
LB17


1976.
LA72
LB17


1977.
LA73
LB17


1978.
LA74
LB17


1979.
LA75
LB17


1980.
LA76
LB17


1981.
LA77
LB17


1982.
LA78
LB17


1983.
LA79
LB17


1984.
LA80
LB17


1985.
LA81
LB17


1986.
LA82
LB17


1987.
LA83
LB17


1988.
LA84
LB17


1989.
LA85
LB17


1990.
LA86
LB17


1991.
LA87
LB17


1992.
LA88
LB17


1993.
LA89
LB17


1994.
LA90
LB17


1995.
LA91
LB17


1996.
LA92
LB17


1997.
LA93
LB17


1998.
LA94
LB17


1999.
LA95
LB17


2000.
LA96
LB17


2001.
LA97
LB17


2002.
LA98
LB17


2003.
LA99
LB17


2004.
LA100
LB17


2005.
LA101
LB17


2006.
LA102
LB17


2007.
LA103
LB17


2008.
LA104
LB17


2009.
LA105
LB17


2010.
LA106
LB17


2011.
LA107
LB17


2012.
LA108
LB17


2013.
LA109
LB17


2014.
LA110
LB17


2015.
LA111
LB17


2016.
LA112
LB17


2017.
LA113
LB17


2018.
LA114
LB17


2019.
LA115
LB17


2020.
LA116
LB17


2021.
LA117
LB17


2022.
LA118
LB17


2023.
LA119
LB17


2024.
LA1
LB18


2025.
LA2
LB18


2026.
LA3
LB18


2027.
LA4
LB18


2028.
LA5
LB18


2029.
LA6
LB18


2030.
LA7
LB18


2031.
LA8
LB18


2032.
LA9
LB18


2033.
LA10
LB18


2034.
LA11
LB18


2035.
LA12
LB18


2036.
LA13
LB18


2037.
LA14
LB18


2038.
LA15
LB18


2039.
LA16
LB18


2040.
LA17
LB18


2041.
LA18
LB18


2042.
LA19
LB18


2043.
LA10
LB18


2044.
LA21
LB18


2045.
LA22
LB18


2046.
LA23
LB18


2047.
LA24
LB18


2048.
LA25
LB18


2049.
LA26
LB18


2050.
LA27
LB18


2051.
LA28
LB18


2052.
LA29
LB18


2053.
LA30
LB18


2054.
LA31
LB18


2055.
LA32
LB18


2056.
LA33
LB18


2057.
LA34
LB18


2058.
LA35
LB18


2059.
LA36
LB18


2060.
LA37
LB18


2061.
LA38
LB18


2062.
LA39
LB18


2063.
LA40
LB18


2064.
LA41
LB18


2065.
LA42
LB18


2066.
LA43
LB18


2067.
LA44
LB18


2068.
LA45
LB18


2069.
LA46
LB18


2070.
LA47
LB18


2071.
LA48
LB18


2072.
LA49
LB18


2073.
LA50
LB18


2074.
LA51
LB18


2075.
LA52
LB18


2076.
LA53
LB18


2077.
LA54
LB18


2078.
LA55
LB18


2079.
LA56
LB18


2080.
LA57
LB18


2081.
LA58
LB18


2082.
LA59
LB18


2083.
LA60
LB18


2084.
LA61
LB18


2085.
LA62
LB18


2086.
LA63
LB18


2087.
LA64
LB18


2088.
LA65
LB18


2089.
LA66
LB18


2090.
LA67
LB18


2091.
LA68
LB18


2092.
LA69
LB18


2093.
LA70
LB18


2094.
LA71
LB18


2095.
LA72
LB18


2096.
LA73
LB18


2097.
LA74
LB18


2098.
LA75
LB18


2099.
LA76
LB18


2100.
LA77
LB18


2101.
LA78
LB18


2102.
LA79
LB18


2103.
LA80
LB18


2104.
LA81
LB18


2105.
LA82
LB18


2106.
LA83
LB18


2107.
LA84
LB18


2108.
LA85
LB18


2109.
LA86
LB18


2110.
LA87
LB18


2111.
LA88
LB18


2112.
LA89
LB18


2113.
LA90
LB18


2114.
LA91
LB18


2115.
LA92
LB18


2116.
LA93
LB18


2117.
LA94
LB18


2118.
LA95
LB18


2119.
LA96
LB18


2120.
LA97
LB18


2121.
LA98
LB18


2122.
LA99
LB18


2123.
LA100
LB18


2124.
LA101
LB18


2125.
LA102
LB18


2126.
LA103
LB18


2127.
LA104
LB18


2128.
LA105
LB18


2129.
LA106
LB18


2130.
LA107
LB18


2131.
LA108
LB18


2132.
LA109
LB18


2133.
LA110
LB18


2134.
LA111
LB18


2135.
LA112
LB18


2136.
LA113
LB18


2137.
LA114
LB18


2138.
LA115
LB18


2139.
LA116
LB18


2140.
LA117
LB18


2141.
LA118
LB18


2142.
LA119
LB18









In one embodiment, the compound is selected from the group consisting of:






















In one embodiment, 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, comprising a compound having the formula Ir(LA)n(LB)3-n, having the structure according to Formula I




is provided. In the compound of Formula I, A1, A2, A3, A4, A5, A6, A7, and A8 comprise carbon or nitrogen, and at least one of A1, A2, A3, A4, A5, A6, A7, and A8 is nitrogen. Ring B is bonded to ring A through a C—C bond, the iridium is bonded to ring A through a Ir—C bond. X is O, S, or Se. R1, R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution, and any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring. R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.

In one embodiment, the first device is a consumer product. In one embodiment, the first device is an organic light-emitting device. In one embodiment, the first device comprises a lighting panel.
In another embodiment, the organic layer in the first organic light emitting device is an emissive layer and the compound is an emissive dopant. In one embodiment, the organic layer is an emissive layer and the compound is a non-emissive dopant.
In one embodiment, the organic layer further comprises a host. In one embodiment, the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host 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≡CHCnH2n+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 one embodiment, the host comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
The “aza” designation in the fragments described above, i.e. aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
In one embodiment, the host is selected from a group of compounds, the Host Group, consisting of:










and combinations thereof.

In one embodiment, the host comprises a metal complex.
According to an aspect of the present disclosure, the compound according to Formula I wherein A1-A4 and A6-A8 are C and A5 is N and having a structure according to Formula II




is also provided. In the compound of Formula II, X, R1, R2, R3, and R4, and n are as defined for Formula I. R is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof; R1 represent mono-, di-substitution, or no substitution.

In one embodiment, n in the compound of Formula II is 1. In one embodiment, X is O. In one embodiment, R is alkyl. In one embodiment, R is cycloalkyl. In one embodiment, R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof. In one embodiment, R1, R2, R3, and R4 can be independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof. In one embodiment, R2 is alkyl, or partially or fully deuterated alkyl. In one embodiment, R3 is alkyl, or partially or fully deuterated alkyl.
In one embodiment, LA in Formula II is selected from the group consisting of






















































































































The LB in Formula II is selected from the group consisting of:
















In one embodiment, the compound of Formula II is selected from the group consisting of:






























































































































































































































































































According to another aspect, the organic layer in the first device described above can comprise a compound having the formula Ir(LA)n(LB)3-n, having the structure according Formula II as defined above.
According to another aspect, a formulation comprising the compound of Formula I and/or Formula II is also within the scope of the present disclosure.
Device Examples
All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode is 1200 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices are encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication, and a moisture getter was incorporated inside the package.
The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of Compound B as the hole injection layer (HIL), 300 Å of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) as the hole transporting layer (HTL), 300 Å of the compound of Formula I doped in with Compound C as host, with 10-15 wt % of the iridium phosphorescent compound as the emissive layer (EML), 50 {acute over (Å)} of Compound C as a blocking layer (BL), 450 Å of tris-8-hydroxyquinoline aluminum (Alq) as the ETL. The comparative Example with Compound A was fabricated similarly to the Device Examples except that Compound A was used as the emitter in the EML.
The device results and data comparing the compounds of Formula I to the comparative compounds are summarized in Tables 2 and 3. The device results and data comparing the compounds of Formula II to the comparative compounds are summarized in Tables 4 and 5. As used herein, NPD, Alq, and comparative Compounds A to D have the following structures:














TABLE 2







device Structures of Inventive Compound and Comparative Compound













HIL
HTL
EML
BL
ETL


Example
(100 Å)
(300 Å)
(300 Å, doping %)
(50 Å)
(450 Å)
















Comparative
Compound B
NPD
Compound C
Compound A
Compound C
Alq


Example 1



10%


Inventive
Compound B
NPD
Compound C
Compound 1
Compound C
Alq


Example 1



10%


Comparative
Compound B
NPD
Compound C
Compound D
Compound C
Alq


Example 2



10%


Inventive
Compound B
NPD
Compound C
Compound
Compound C
Alq


Example 2



105 10%


Inventive
Compound B
NPD
Compound C
Compound 4
Compound C
Alq


Example 3



10%
















TABLE 3







VTE Device Results











1931
At 1000 nits
At 40 mA/cm2

















CIE
λmax
FWHM
Voltage
LE
EQE
PE
L0
LT80

















Example
x
y
(nm)
(nm)
(V)
(Cd/A)
(%)
(lm/W)
(nits)
(h)




















Comparative
0.350
0.619
530
62
6.2
64.8
17.2
33
18,482
121


Example 1


Inventive
0.340
0.625
526
60
5.9
61.9
16.5
32.9
18,466
184


Example 1


Comparative
0.319
0.618
520
74
6.2
51
14.4
25.9
15,504
65


Example 2


Inventive
0.298
0.621
514
72
6.5
39.9
11.5
19.9
12,605
41


Example 2


Inventive
0.343
0.623
528
62
6.8
47.1
12.5
21.8
13,471
370


Example 3









Table 2 summarizes the performance of the devices. The driving voltage (V), luminous efficiency (LE), external quantum efficiency (EQE) and power efficiency (PE) are shown at 1000 nits. LT80 was measured under a constant current density of 40 mA/cm2 at the initial luminance (L0).

As can be seen from the table, the EL peak of Compound 1 was at 526 nm, which is 4 nm blue shifted compared to that of Compound A. This is also consistent with the PL spectra. Both compounds showed very narrow FWHMs (full width at half maximum) at 60 and 62 nm, respectively. Both compounds showed high EQE in the same structure. The driving voltage of Compound 1 at 1000 nits is slightly lower than that of compound A, 5.9 V vs. 6.2 V. Devices incorporating compounds of Formula I, such as Compound 1, also had longer device lifetimes than devices that used Compound A (184 h vs. 121 h). Compound 4 also displayed a 2 nm blue shift relative to Compound A (528 vs. 530 nm). Additionally the LT80 of Compound 4 is significantly longer than that of Compound A (370 vs. 121 h). Compound 105 was also blue shifted compared to Comparative Compound D (514 nm vs. 520 nm). The color of Compound 105 was also more saturated. Compounds of Formula I have unexpected and desirable properties for use as saturated green emitters in OLEDs.
Device Data for Compounds of Formula II:
The organic stack of the device examples consisted of sequentially, from the ITO surface, 100 Å of Compound B as the hole injection layer (HIL), 300 Å of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) as the hole transporting layer (HTL), 300 Å of the invention compound doped in Compound C as host with as the emissive layer (EML), 50 Å of Compound C as blocking layer, 450 Å of tris-8-hydroxyquinoline aluminum (Alq) as the ETL. In order to show Comparative Example using a compound having Formula I, Compound 4, was fabricated similarly to the Device Examples except that the Compound 4 was used as the emitter in the EML.
The device results and data are summarized in Tables 4 and 5 below.







TABLE 4







device Structures of Inventive Compound and Comparative Compound.


The thickness of each layer is provided.













HIL
HTL

BL
ETL


Example
(100 Å)
(300 Å)
EML (300 Å, doping %)
(50 Å)
(450 Å)
















Comparative
Compound B
NPD
Compound C
Compound 4
Compound C
Alq


Example 3



7%


Inventive
Compound B
NPD
Compound C
Compound II-1
Compound C
Alq


Example 4



7%


Inventive
Compound B
NPD
Compound C
Compound II-49
Compound C
Alq


Example 5



7%


Inventive
Compound B
NPD
Compound C
Compound II-355
Compound C
Alq


Example 6



7%


Comparative
Compound B
NPD
Compound C
Compound E
Compound C
Alq


Example 4



7%


Comparative
Compound B
NPD
Compound C
Compound F
Compound C
Alq


Example 5
















TABLE 5







VTE Device Results













1931
λ

At 1,000 nits
40 mA/cm2

















CIE
max
FWHM
Voltage
LE
EQE
PE
Lo
LT80%

















Example
x
y
[nm]
[nm]
relative
relative
relative
relative
[nits]
relative




















Comparative
0.342
0.623
526
60
1
1
1
1
16,133
1


Example 3


Inventive
0.362
0.611
530
66
0.98
1.14
1.13
1.15
18,749
1.2


Example 4


Inventive
0.352
0.616
528
62
0.97
1.03
1.03
1.05
16,537
1.64


Example 5


Inventive
0.365
0.609
530
64
0.95
1.28
1.28
1.34
17,522
1.53


Example 6


Comparative
0.351
0.62
528
62
0.97
0.86
0.85
0.88
15,467
0.6


Example 4


Comparative
0.344
0.621
526
64
0.98
0.79
0.78
0.79
13,896
1.16


Example 5









Table 5 summarizes the performance of the devices. The driving voltage (V), luminous efficiency (LE), external quantum efficiency (EQE) and power efficiency (PE) are shown at 1000 nits, while the lifetime (LT80%) was defined as the time required for the device to decay to 80% of its initial luminance (L0) under a constant current density of 40 mA/cm2. All measured values are listed as relative to the comparative example which is denoted as 1. As shown in Table 5 all three inventive compounds required slightly less driving voltage (0.98, 0.97 and 0.95) relative to the comparative compound (1.0). The inventive compounds demonstrated superior efficiency in all three categories also: the relative LE values were 1.14, 1.03 and 1.28 for the Inventive Examples 4, 5 and 6, respectively, compared to 1.0 for Comparative Example 3 and 0.86 and 0.79 for Comparative Examples 4 and 5, respectively. The relative EQE of values were 1.13, 1.03 and 1.28 for Inventive Examples 4, 5 and 6, respectively, compared to 1.0 for Comparative Example 3 and 0.85 and 0.78 for Comparative Examples 4 and 5, respectively. The relative PE values were 1.15, 1.05, 1.34 for the Inventive Examples 4, 5 and 6, respectively, compared to 1.0 for the Comparative Example 3 and 0.88 and 0.79 for Comparative Examples 4 and 5, respectively. Finally the superior device stability of the inventive compounds were shown by the relative LT80 values of 1.20, 1.64, 1.53 for the Inventive Examples 4, 5, and 6, respectively compared to 1.0 for the Comparative Example 3 and 0.6 for Comparative Example 4.
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 porphryin 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 sliane 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:




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:




Met is a metal; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is 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, (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:




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 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:




(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 atome, 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:







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 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:




k is an integer from 1 to 20; L101 is 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:







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:




(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, exciton/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 4 below. Table 4 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.









TABLE 4





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 sliane 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)


 


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EXPERIMENTAL
Chemical abbreviations used throughout the text are as follows: DME is dimethoxyethane, THF is tetrahydrofuran, DCM is dichloromethane, DMSO is dimethyl sulfoxide, dba is dibenzylidineacetone.
Synthesis of Compound 1
Preparation of 2-(3-bromopyridin-2-yl)-6-chlorophenol




(3-Chloro-2-hydroxyphenyl)boronic acid (5.0 g, 29.0 mmol) and 2,3-dibromopyridine (6.87 g, 29.0 mmol) were added to a 500 mL 2-necked flask. The reaction mixture was diluted with DME (120 mL) and water (90 mL) with the potassium carbonate (8.02 grams, 58.0 mmol) dissolved in it. This mixture was degassed for 10 minutes before addition of Pd(PPh3)4 (1.00 grams, 3 mol %). The reaction mixture was then stirred at gentle reflux for 5 hours. The reaction mixture was then diluted with ethyl acetate and brine. The organic layer was washed with brine and dried over sodium sulfate. The product was purified using silica gel column chromatography using a mobile phase gradient of 5-10% ethyl acetate in hexane to obtain 2.8 grams (34%) of a white solid.
Preparation of 6-chlorobenzofuro[3,2-b]pyridine




Into a 500 mL round-bottomed flask was placed 2-(3-bromopyridin-2-yl)-6-chlorophenol (4.5 g, 15.82 mmol), copper(I) iodide (0.602 g, 3.16 mmol), picolinic acid (0.779 g, 6.33 mmol) and potassium phosphate (6.71 g, 31.6 mmol) and DMSO (150 mL). This mixture was stirred in an oil bath at 125° C. for 5 hours. The heat was removed and the mixture was diluted with ethyl acetate and filtered through Celite®. The filtrate was washed with brine twice then with water. The organic layer was adsorbed onto Celite® and chromatographed eluting with 40-100% dichloromethane in hexane to obtain 2.45 grams (76%) of the desired product as a white solid.
Preparation of 6-(pyridin-2-yl)benzofuro[3,2-b]pyridine




2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (1.12 g, 2.36 mmol), 6-chlorobenzofuro[3,2-b]pyridine (3.0 g, 14.73 mmol), and Pd2 dba3 (0.54 g, 0.59 mmol) were added to a 250 mL 3-necked flask. The atmosphere in the flask was evacuated and backfilled with nitrogen. THF (15 mL) was added by syringe to the reaction flask. Pyridin-2-yl zinc(II) bromide (44.2 mL, 22.10 mmol) was then added and the flask was stirred in an oil bath at 75° C. After 2 hours, the reaction mixture was cooled and diluted with aqueous sodium bicarbonate and ethyl acetate. The aqueous layer was extracted with ethyl acetate and the combined organic layers were dried with sodium sulfate. The crude product was purified using silica gel column chromatography eluted with 0-5% methanol in DCM to give 3.2 g (88%) of desired product. This product was further purified by column chromatography over silica gel using DCM followed by up to 40% ethyl acetate/DCM mixture as eluent to obtain 2.8 g (77%) 6-(pyridin-2-yl)benzofuro[3,2-b]pyridine as a white solid.
Preparation of Compound 1




6-(Pyridin-2-yl)benzofuro[3,2-b]pyridine (2.71 g, 11.00 mmol) and iridium complex (1.964 g, 2.75 mmol) were added to ethanol (90 mL) and degassed for 15 minutes with nitrogen. The reaction mixture was heated to reflux until the iridium triflate intermediate disappeared. The reaction mixture was cooled to room temperature and filtered through a Celite® plug and washed with ethanol and hexanes. The yellow color precipitate was dissolved in DCM. Solvents were removed under reduced pressure from the DCM solution to give 1.65 g of crude material which was purified by silica gel column chromatography using 1:1 DCM/hexanes (v/v) followed by 95:5 DCM/methanol (v/v) as eluent. The isolated material was further purified by reversed phase column chromatography over C18 stationary phase using 95:5% acetonitrile/water as eluent to give 0.7 g (34%) of Compound 1.
Synthesis of Compound 4
Preparation of 3-(2,3-dimethoxyphenyl)pyridin-2-amine




3-Bromopyridin-2-amine (23.77 g, 137 mmol), (2,3-dimethoxyphenyl)boronic acid (25 g, 137 mmol), and Pd(Ph3P)4 (4.76 g, 4.12 mmol) were added to a 2 L 2-necked flask. The reaction mixture was diluted with THF (600 mL). A solution of water (300 mL) with sodium carbonate (14.56 g, 137 mmol) dissolved in it was then added. This mixture was degassed and stirred at reflux for 20 hours. The mixture was then diluted with ethyl acetate and brine. The organic layer was washed with water and dried over sodium sulfate. The product was chromatographed on a silica gel column eluted with 0-50% ethyl acetate in DCM to obtain 28.9 g (91%) of the desired material.
Preparation of 8-methoxybenzofuro[2,3-b]pyridine




3-(2,3-Dimethoxyphenyl)pyridin-2-amine (14 g, 60.8 mmol) was added to a 500 mL round bottom flask. Acetic acid (220 mL) and THF (74 mL) were added. This mixture was stirred in a salt water ice bath. t-Butyl nitrite (14.5 mL, 109 mmol) was added drop-wise. The reaction mixture was stirred in the bath for 3 hours and then was allowed to warm ambient temperature with stirring. This mixture was evaporated in vacuo and partitioned between ethyl acetate and aqueous sodium bicarbonate. The product was chromatographed on silica gel. Elution with 25% ethyl acetate in hexane gave 6.61 g (54.6%) of 8-methoxybenzofuro[2,3-b]pyridine as a white solid.
Preparation of benzofuro[2,3-b]pyridin-8-ol




8-Methoxybenzofuro[2,3-b]pyridine (6.6 g, 33.1 mmol) was added along with pyridine HCl (25 g) to a 250 mL round bottom flask. This mixture was stirred in an oil bath at 200° C. for 10 hours. Aqueous sodium bicarbonate and DCM were added to the mixture. The organic layer was dried and evaporated to a brown solid to obtain 5.07 g (83%) of the desired product.
Preparation of benzofuro[2,3-b]pyridin-8-yl trifluoromethanesulfonate




Benzofuro[2,3-b]pyridin-8-ol (5.5 g, 29.7 mmol) was added to a 500 mL round bottom flask and DCM (250 mL) was added. Pyridine (6.01 mL, 74.3 mmol) was added and the flask was placed in an ice bath. Triflic anhydride (7.5 mL, 44.6 mmol) was dissolved in DCM (30 mL) and added drop-wise over 10 min. The bath was removed and the reaction was allowed to warm to ambient temperature and stirred overnight. The solution was washed with saturated sodium bicarbonate solution then water. The product was chromatographed on a silica gel column, which was eluted with DCM to obtain 8.1 g (86%) of the desired product as a white solid was obtained.
Preparation of 8-(pyridin-2-yl)benzofuro[2,3-b]pyridine




Benzofuro[2,3-b]pyridin-8-yl trifluoromethanesulfonate (4 g, 12.61 mmol), X-Phos (0.481 g, 1.009 mmol) and Pd2 dba3 (0.231 g, 0.252 mmol) were added to a 250 mL 3-necked flask. The atmosphere in the flask was evacuated and backfilled with nitrogen. THF (40 mL) and pyridin-2-yl zinc(II) bromide (37.8 mL, 18.91 mmol) were added. This mixture was stirred in an oil bath at 70° C. for 4 hours. The mixture was filtered through Celite®, and the filter cake was washed with ethyl acetate. The crude material was adsorbed on to Celite® and chromatographed on a silica gel column eluted with 25-50% ethyl acetate in hexane to obtain 2.7 g (87%) of the desired product as a white solid.
Preparation of Compound 4




8-(Pyridin-2-yl)benzofuro[2,3-b]pyridine (3.8 g, 15.4 mmol) and iridium complex (3.67 g, 5.10 mmol) were combined in a 500 mL round bottom flask. 2-Ethoxyethanol (125 mL) and dimethylformamide (125 mL) were each added and the mixture was stirred in an oil bath at 135° C. for 18 hours. The mixture was concentrated first on a rotary evaporator then on a Kugelrohr apparatus. The residue was purified on a silica gel column eluted with 0-3% ethyl acetate in dichloromethane to afford 2.48 g (65%) of the desired product as yellow solid.
Synthesis of Compound 105
Preparation of 2-(5-chloro-2-methoxyphenyl)pyridin-3-amine




(5-Chloro-2-methoxyphenyl)boronic acid (12 g, 64.4 mmol), 2-bromopyridin-3-amine (11.14 g, 64.4 mmol) potassium carbonate (17.79 g, 129 mmol) and Pd(Ph3P)4 (3.72 g, 3.22 mmol) were added to a 1 L 3-necked flask. The reaction mixture was diluted with DME (300 mL) and water (150 mL). This mixture was stirred at reflux for 3 hours. The mixture was filtered through Celite® and the filter cake was washed with ethyl acetate. Water was added and the layers were separated. The organic layer was chromatographed on a silica gel column which was eluted with 0-10% ethyl acetate in DCM to give 10.9 g (72%) of the desired compound.
Preparation of 8-chlorobenzofuro[3,2-b]pyridine




In a 1 L round-bottomed flask was placed 2-(5-chloro-2-methoxyphenyl)pyridin-3-amine (10.9 g, 46.4 mmol) and THF (85 mL). Tetrafluoroboric acid (85 mL, 678 mmol) was added along with water (50 mL). The flask was placed in an ethylene glycol-dry ice bath. Sodium nitrite (6.73 g, 98 mmol) was dissolved water (30 mL) and added drop-wise to the flask. The solution turned from yellow to orange with evolution of gas. This reaction mixture was stirred in the bath for 4 hours, and allowed to warm to ambient temperature. Aqueous saturated sodium bicarbonate (500 mL) was added. The product was extracted with DCM and chromatographed on a 200 gram silica gel column eluted with 20-40% ethyl acetate in hexane to obtain 3.26 g (34.5%) of the desired product as a white solid.
Preparation of 8-(pyridin-2-yl)benzofuro[3,2-b]pyridine




8-Chlorobenzofuro[3,2-b]pyridine (3.2 g, 15.72 mmol) and Pd2 dba3 (0.288 g, 0.314 mmol) and X-Phos (0.599 g, 1.257 mmol) were added to a 250 mL 3-necked flask. The atmosphere in the flask was evacuated and backfilled with nitrogen. THF (40 mL) was added. Next, pyridin-2-yl zinc(II) bromide (47.1 mL, 23.57 mmol) was added. This mixture was stirred in an oil bath at 70° C. for 4 hours. The mixture was then diluted with aqueous sodium bicarbonate and ethyl acetate. This mixture was filtered through Celite®, and the organic and aqueous layers were separated. The aqueous layer was extracted once more with ethyl acetate. The combined organic layers were chromatographed on a 150 gram silica gel column eluted first with 20% ethyl acetate in hexane then 10% ethyl acetate in DCM and finally 2.5% methanol in DCM. The eluent triturated in hexane and filtered giving 3.2 g (83%) of the desired product as a beige powder.
Preparation of Compound 105




Iridium complex (2.99 g, 4.20 mmol) and 8-(pyridin-2-yl)benzofuro[3,2-b]pyridine (3.1 g, 12.59 mmol) were each added to a 250 mL round bottom flask. 2-Ethoxyethanol (50 mL) and dimethylformamide (50 mL) were added and this was stirred in an oil bath at 150° C. for 18 hours. The flask was placed on a Kugelrohr apparatus and the solvents were removed. The crude material was chromatographed on a silica gel column eluted with 0-10% ethyl acetate in DCM to obtain 2.07 g (66%) of the desired compound.
Synthesis of Compound II-1
Preparation of 3-(2,3-dimethoxyphenyl)-6-methylpyridin-2-amine




A solution of 3-bromo-6-methylpyridin-2-amine (12.33 g, 65.9 mmol) and (2,3-dimethoxyphenyl)boronic acid (12.0 g, 65.9 mmol), Pd(PPh3)4 (2.286 g, 1.978 mmol) and sodium carbonate (6.99 g, 65.9 mmol) in DME (250 ml) and water (125 ml) was stirred at reflux for 5 h. The crude mix was filtered through celite and the solid was washed with ethyl acetate. The filtrate was washed with brine and the solvent was evaporated. The crude product was purified by column chromatography on silica gel with 0-5% methanol in DCM as eluent to obtain 14.5 grams (90%) of the desired product as a cream colored solid.
Preparation of 8-methoxy-2-methylbenzofuro[2,3-b]pyridine




Into a solution of 3-(2,3-dimethoxyphenyl)-6-methylpyridin-2-amine (14.5 g, 59.4 mmol) in acetic acid (200 ml) and THF (67 ml) was added dropwise tert-butylnitrite (14.1 ml, 106.9 mmol) at 0° C. After stirring at this temperature for 2 h, the reaction mixture was allowed to warm to room temperature. Upon evaporation off the solvent, the residue was partitioned between ethyl acetate and water. The organic phase was isolated, washed with aqueous sodium bicarbonate and brine, dried over sodium sulfate. Upon evaporation off the solvent, the residue was purified by column chromatography on silica gel with 25% ethyl acetate in hexane to obtain 7.65 g (60.4%) of desired product as a pale yellow solid.
Preparation of 2-methylbenzofuro[2,3-b]pyridin-8-ol




A mixture of 8-methoxy-2-methylbenzofuro[2,3-b]pyridine (7.6 g, 35.6 mmol) and pyridine hydrochloride (25 g, 216 mmol) was heated at 200° C. for 15 h. After cooling to room temperature, the solid was sonicated with aqueous sodium bicarbonate solution. The solid was isolated by filtration to yield 6.72 g (95%) of desired product as a brown powder.
Preparation of 2-methylbenzofuro[2,3-b]pyridin-8-yltrifluoromethanesulfonate




Into a suspension of 2-methylbenzofuro[2,3-b]pyridin-8-ol (6.7 g, 33.6 mmol) in dichloromethane (300 ml) was added dropwise a solution of trifluoromethanesulfonic anhydride (8.47 ml, 50.5 mmol) in dichloromethane (30 ml) at 0° C. After stirring overnight, the reaction was quenched with saturated sodium bicarbonate. The organic phase was isolated, washed with brine and dried over sodium sulfate. Upon evaporation off the solvent, the crude product was purified by column chromatography on silica gel with dichloromethane as eluent to obtain 8.95 g (80%) of desired product as a pale yellow solid.
Preparation of 2-methyl-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine




Into a solution of 2-methylbenzofuro[2,3-b]pyridin-8-yl trifluoromethanesulfonate (4 g, 12.07 mmol), Pd2 dba3 (0.221 g, 0.241 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.230 g, 0.483 mmol) in THF (80 ml) was added a solution of pyridin-2-ylzinc(II) bromide (36.2 ml, 0.5 M, 18.11 mmol) in THF at 60° C. It was stirred at 65° C. for 12 h and quenched with saturated ammonium chloride solution. The organic phase was isolated, diluated with ethyl acetate, washed with brine, and dried over magnesium sulfate. Upon evaporation off the solvent, the residue was purified by column chromatography on silica gel with 5-20% ethyl acetate in dichlomethane as eluent to yield 2.05 g (65%) of desired product as a white solid.
Preparation of Compound II-1




Iridium complex (1.828 g, 2.56 mmol) and 2-methyl-8-(pyridine-2-yl)benzofuro[2,3-b]pyridine (2 g, 7.68 mmol) were added to 85 mL ethanol and the reaction mixture was heated to reflux for 20 h. The reaction mixture was cooled, filtered through a Celite® pad and the filtrate was discarded. Collected precipitate was washed with ethanol, dried and purified by column chromatography on silica gel with dichloromethane as eluent to yield 0.9 g (46%) of Compound II-1 as a yellow solid.
Synthesis of Compound II-49
Preparation of 2-d3-methyl-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine




A solution of 2-methyl-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine (6.3 g, 24.20 mmol) and sodium ethoxide (3.29 grams, 48.4 mmol) in ethanol-D (100 ml) was refluxed for 72 h. The solvent was evaporated and the residue was partitioned between ethyl acetate and water. The organic phase was isolated, dried over sodium sulfate and evaporated. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with 0-15% ethyl acetate in dichloromethane to yield 5.1 g (80%) of desired compound as a white solid.
Preparation of Compound II-49




A solution of 2-d3-methyl-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine (3.8 grams, 14.4 mmol) and iridium complex (3.43 grams, 4.81 mmol) in DMF (100 ml) and 2-ethoxyethanol (100 ml) were heated at 130° C. for 18 h. Upon evaporation off the solvent, the crude product was purified by column chromatography on silica gel with 65-100% dichloromethane in hexane to yield 2.77 g (75%) of Compound II-49 as a yellow solid.
Preparation of Compound II-355




A solution of 2-d3-methyl-8-(pyridin-2-yl)benzofuro[2,3-b]pyridine (4.45 g, 16.90 mmol) and iridium complex (4.21 g, 5.63 mmol) in DMF (100 ml) and 2-ethoxyethanol (100 ml) was heated at 130° C. under nitrogen for 18 h. Upon evaporation off the solvent, the crude product was purified by column chromatography on silica gel with 70-100% dichloromethane in hexane to yield 3.30 g (74%) of Compound II-355 as a yellow solid.
Synthesis of Compound II-7
Preparation of 2-methyl-8-(4-methylpyridin-2-yl)benzofuro[2,3-b]pyridine




Into a solution of 2-methylbenzofuro[2,3-b]pyridin-8-yltrifluoromethanesulfonate (4.45 g, 13.43 mmol), dicyclohexyl(2′,4′,6′-triisopropyl-[1′,1′-biphenyl]-2-yl)phosphine (0.512 g, 1.075 mmol) and Pd2 dba3 (0.246 g, 0.269 mmol) in THF 50 ml was added a solution of 4-methyl-2-pyridylzinc bromide solution (50 ml, 0.5 M, 25 mmol). The reaction mixture was heated at 60-65° C. under nitrogen for 12 h and quenched with saturated sodium bicarbonate solution. The suspension was filtered through a short plug of Celite®. The filtrate was washed with brine and dried over magnesium sulfate. Upon evaporation off the solvent, the residue was purified by column chromatography on silica gel with 25-50% ethyl acetate in dichlomethane as eluent to yield 3.02 g (82%) of desired product as a white solid.
Preparation of Compound II-7




A solution of iridium complex (2.60 g, 3.65 mmol) and 2-methyl-8-(4-methylpyridin-2-yl)benzofuro[2,3-b]pyridine (3.0 g, 10.94 mmol) in ethanol (120 ml) was refluxed for 24 h. After cooling to room temperature, the solic was collected by filtration and purified by column chromatography on silica gel with 65-100% DCM in hexane to yield 1.5 g (53%) of Compound 7 as a yellow solid.
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 compound having a structure Ir(LA)n(LB)3-n according to Formula II



wherein R is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, any of which may be partially or fully deuterated;
wherein R1 represent mono-, di-substitution, or no substitution;
wherein R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
wherein any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring;
wherein R1, R2, R3, and R4 are 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 X is O, S, or Se; and
wherein n is an integer from 1 to 3.

2. The compound of claim 1, wherein n is 1.

3. The compound of claim 1, wherein X is O.

4. The compound of claim 1, wherein R is alkyl.

5. The compound of claim 1, wherein R is cycloalkyl.

6. The compound of claim 1, wherein R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

7. The compound of claim 1, wherein R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof.

8. The compound of claim 1, wherein R2 is alkyl, or partially or fully deuterated alkyl.

9. The compound of claim 1, wherein R3 is alkyl, or partially or fully deuterated alkyl.

10. The compound of claim 1, wherein R1, R2, R3, and R4 are H.

11. The compound of claim 10, wherein R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

12. The compound of claim 10, wherein R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, and partially or fully deuterated variants thereof.

13. The compound of claim 1, wherein R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof.

14. The compound of claim 13, wherein R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, partially or fully deuterated variants thereof, and combinations thereof.

15. The compound of claim 1, wherein LA is selected from the group consisting of:

16. The compound of claim 15, wherein R3 and R4 are independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof.

17. The compound of claim 15, wherein R3 and R4 are H.

18. The compound of claim 1, wherein LB is selected from the group consisting of:

19. The compound of claim 1, wherein the compound is selected from the group consisting of:

20. A first device comprising a 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 Ir(LA)n(LB)3-n, having the structure:




wherein X is O, S, or Se;
wherein R is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, any of which may be partially or fully deuterated;
wherein R1 represent mono-, di-substitution, or no substitution;
wherein R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
wherein any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring;
wherein R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.

21. The first device of claim 20, wherein the first device is a consumer product.

22. The first device of claim 20, wherein the first device is an organic light-emitting device.

23. The first device of claim 20, wherein the first device comprises a lighting panel.

24. The first device of claim 20, wherein the organic layer is an emissive layer and the compound is an emissive dopant.

25. The first device of claim 20, wherein the organic layer is an emissive layer and the compound is a non-emissive dopant.

26. The first device of claim 20, wherein the organic layer further comprises a host.

27. The first device of claim 26, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan;
wherein any substituent in the host 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≡CHCnH2n+1, Ar1, Ar1-Ar2, and CnH2n—Ar1;
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.

28. The first device of claim 26, wherein the host comprises at least one chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

29. The first device of claim 26, wherein the host is selected from the group consisting of:







and combinations thereof.

30. The first device of claim 26, wherein the host comprises a metal complex.

31. A formulation comprising a compound having the formula Ir(LA)n(LB)3-n, having the structure:



wherein X is O, S, or Se;
wherein R is selected from the group consisting of alkyl, cycloalkyl, and combinations thereof, any of which may be partially or fully deuterated;
wherein R1 represents mono-, di-substitution or no substitution;
wherein R2, R3, and R4 independently represent mono-, di-, tri-, tetra-substitution, or no substitution;
wherein any adjacent substitutions in R1, R2, R3, and R4 are optionally linked together to form a ring;
wherein R1, R2, R3, and R4 are 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 n is an integer from 1 to 3.