# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

Heteroleptic cyclometallated complexes having a 6-membered ring cyclometallated to the metal, as shown in Formula (I), are provided:




wherein ring A and ring B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; wherein L1 is BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, or GeRR; wherein Z1 and Z2 are independently carbon or nitrogen; wherein at least one of Z1 and Z2 is carbon; wherein





is a bidentate ligand selected from the group consisting of:





wherein R1, R2, Ra, Rb, Rc, and Rd may represent mono, di, tri, or tetra substitution, or no substitution; wherein R1, R2, R, R′, Ra, Rb, Rc, and Rd are each independently selected from various substituents; and wherein n is 1 or 2. Devices, such as organic light emitting devices (OLEDs) that comprise phosphorescent light emitting materials are also provided.

## Background
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 organic light emitting devices (OLEDs). More specifically, the invention relates to phosphorescent light emitting materials that may have improved electron stability.
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 new type of light emitting material is provided, which include heteroleptic complexes having a cyclometallated 6-membered ring, as shown in Formula (I), below:




wherein ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; wherein L1 is BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, or GeRR′; wherein Z1 and Z2 are independently carbon or nitrogen; wherein at least one of Z1 and Z2 is carbon; wherein





is a bidentate ligand selected from the group consisting of:





wherein R1, R2, Ra, Rb, Rc, and Rd may represent mono, di, tri, or tetra substitution, or no substitution; wherein R1, R2, R, R′, Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring and can be further substituted; and wherein n is 1 or 2.

In some such embodiments,




where the variables have the definitions provided above.

In some such embodiments, A-L1-B is




where the variables have the definitions provided above. In some such embodiments, L1 is CRR′, wherein R and R′ are alkyl. In some further such embodiments, CRR′ is C(CH3)2.

In some embodiments, A-L1-B is:




wherein R6 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, where other variables have the definitions provided above.

In some such embodiments A-L1-B is




wherein R5 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, where the other variables have the definitions provided above.

In some embodiments, the ring A is an imidazole ring, which may be substituted as indicated, and Z1 is nitrogen.
In some such embodiments A-L1-B is




wherein R5 and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, where the other variables have the definitions provided above.

In some embodiments,




and R7 and R8 are alkyl.

Heteroleptic complexes are provided, where the complexes are selected from the group consisting of:





















































































































































































A device is also provided. The device may include an anode, a cathode, and an organic layer disposed between the anode and the cathode, where the organic layer comprises a heteroleptic complex of any of the foregoing embodiments.
The invention is not limited to any particular type of device. In some embodiments, the device is a consumer product. In some embodiments, the device is an organic light emitting device (OLED). In other embodiments, the device comprises a lighting panel.
In some embodiments, the organic layer of the device is an emissive layer. In some such embodiments, the heteroleptic complex is an emissive dopant. In some other embodiments, the heteroleptic complex is a non-emissive dopant.
In some embodiments, the organic layer of the device further comprises a host.
In some such embodiments, 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≡C—CnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions, 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 some such embodiments, the host is a compound selected from the group consisting of:










and combinations thereof.

In some other embodiments, the host comprises a metal complex.
In some other embodiments, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an organic light emitting device.
FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.
FIG. 3 shows a chemical structure that represents a heteroleptic complex having a cyclometallated 6-membered ring, as disclosed herein.
FIG. 4 shows photoluminescence spectra of compounds 1, 59, and X.



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 F.sub.4-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. patent application Ser. No. 10/233,470, now 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.
Heteroleptic complexes having at least one ligand forming a 6-membered ring when cyclometallated to the metal are provided. The inclusion of the cyclometallated 6-membered ring in the complex can provide higher triplet energy, can boost the metal-centered (MC) state compared to the (N,N), (O,O), or (N,O) coordination modes, and can lead to a lower energy LUMO, which improves electron stability. Further, the inclusion of the cyclometallated 6-membered ring can sometimes promote interligand charge transfer and can possibly broaden the emission spectrum of the material, making it suitable for white light applications.
A new type of light emitting material is provided, which include heteroleptic complexes having at least one cyclometallated 6-membered ring, as shown in Formula (I), below:




wherein ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring; wherein L1 is BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, or GeRR′; wherein Z1 and Z2 are independently carbon or nitrogen; wherein at least one of Z1 and Z2 is carbon; wherein





is a bidentate ligand selected from the group consisting of:





wherein R1, R2, Ra, Rb, Rc, and Rd may represent mono, di, tri, or tetra substitution, or no substitution; wherein R1, R2, R, R′, Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; wherein any two adjacent substituents are optionally joined to form a ring and can be further substituted; and wherein n is 1 or 2.

In some such embodiments,




where the variables have the definitions provided above.

In some such embodiments, A-L1-B is




where the variables have the definitions provided above. In some such embodiments, L1 is CRR′, wherein R and R′ are alkyl. In some further such embodiments, CRR′ is C(CH3)2.

In some embodiments, A-L1-B is:




wherein R6 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, where other variables have the definitions provided above.

In some such embodiments A-L1-B is




wherein R5 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, where the other variables have the definitions provided above.

In some embodiments, the ring A is an imidazole ring, which may be substituted as indicated, and Z1 is nitrogen.
In some such embodiments A-L1-B is




wherein R5 and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, where the other variables have the definitions provided above.

In some embodiments,




and R7 and R8 are alkyl.

Heteroleptic complexes are provided, where the complexes are selected from the group consisting of:































































































































A device is also provided. The device may include an anode, a cathode, and an organic layer disposed between the anode and the cathode, where the organic layer comprises a heteroleptic complex of any of the foregoing embodiments.
The invention is not limited to any particular type of device. In some embodiments, the device is a consumer product. In some embodiments, the device is an organic light emitting device (OLED). In other embodiments, the device comprises a lighting panel.
In some embodiments, the organic layer of the device is an emissive layer. In some such embodiments, the heteroleptic complex is an emissive dopant. In some other embodiments, the heteroleptic complex is a non-emissive dopant.
In some embodiments, the organic layer of the device further comprises a host.
In some such embodiments, 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—CnH2+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions, 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 some such embodiments, the host is a compound selected from the group consisting of:










combinations thereof.

In some other embodiments, the host comprises a metal complex.
In some other embodiments, the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
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, compounds 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.
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; X1 to X8 is C (including CH) or N; 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:




M is a metal, having an atomic weight greater than 40; (Y5-Y6) is a bidentate ligand, Y5 and Y6 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y5-Y6) is a 2-phenylpyridine derivative.
In another aspect, (Y5-Y6) is a carbene ligand.
In another aspect, M 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.
In addition to the host materials described above, the device may further comprise other host materials. Examples of such other 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:




M is a metal; (Y3-Y4) is a bidentate ligand, Y3 and Y4 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n 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, M is selected from Ir and Pt.
In a further aspect, (Y3-Y4) 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:







R1 to R7 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above; k is an integer from 0 to 20; X1 to X8 are selected from C (including CH) or N; and Z1 and Z2 are selected from NR1, O, or S.
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 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.
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:




R1 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 0 to 20; X1 to X8 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; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 1 below. Table 1 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.









TABLE 1





MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS















Hole injection materials









Phthalocyanine  and porphryin  compounds




Appl. Phys. Lett. 69, 2160 (1966)


 


Starburst  triarylamines




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


 


CFx Fluoro- hydrocarbon polymer




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


 


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




Synth. Met. 87, 171 (1997) WO2007002683


 


Phosphonic acid  and silane SAMs




US20030162053


 


Triarylamine or polythiophene  polymers with  conductivity  dopants




EP1725079A1


 










 










 


Organic com- pounds with  conductive  inorganic com- pounds, such as  molybdenum and tungsten  oxides




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


 


n-type semi- conducting 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)benzo- thiophene/ (di)benzo- furan




US20070278938, US20080106190 US20110163302


 


Indolo- carbazoles




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- hydroxy- quinolates (e.g., Alq3,  BAlq)




Nature 395, 151 (1998)


 







US20060202194


 







WO2005014551


 







WO2006072002


 


Metal phenoxybenzo- thiazole compounds




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


 


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




Org. Electron. 1, 15 (2000)


 


Aromatic fused  rings




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


 


Zinc complexes




WO2010056066


 


Chrysene based compounds




WO2011086863


 







Green hosts









Arylcarbazoles




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


 







US20030175553


 







WO2001039234


 


Aryltriphenylene compounds




US20060280965


 







US20060280965


 







WO2009021126


 


Poly-fused  heteroaryl compounds




US20090309488 US20090302743 US20100012931


 


Donor acceptor  type molecules




WO2008056746


 







WO2010107244


 


Aza-carbazole/ DBT/DBF




JP2008074939


 







US20100187984


 


Polymers (e.g.,  PVK)




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


 


Spirofluorene  compounds




WO2004093207


 


Metal phenoxybenzo- oxazole compounds




WO2005089025


 







WO2006132173


 







JP200511610


 


Spirofluorene- carbazole compounds




JP2007254297


 







JP2007254297


 


Indolocabazoles




WO2007063796


 







WO2007063754


 


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




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


 







WO2004107822


 


Tetraphenylene  complexes 




US20050112407


 


Metal  phenoxy- pyridine compounds




WO2005030900


 


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




US20040137268, US20040137267


 







Blue hosts









Arylcarbazoles




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


 







US20070190359


 


Dibenzothio- phene/  Dibenzofuran- carbazole compounds




WO2006114966, US20090167162


 







US20090167162


 







WO2009086028


 







US20090030202, US20090017330


 







US20100084966


 


Silicon aryl  compounds




US20050238919


 







WO2009003898


 


Silicon/ Germanium  aryl com- pounds




EP2034538A


 


Aryl benzoyl  ester




WO2006100298


 


Carbazolc linked  by non- conjugated  groups




US20040115476


 


Aza-carbazoles




US20060121308


 


High triplet  metal organometallic  complex




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


 







Phosphorescent dopants


Red dopants









Heavy metal  porphyrins (e.g., PtOEP)




Nature 395, 151 (1998)


 


Iridium(III)  organometallic complexes




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


 







US2006835469


 







US2006835469


 







US20060202194


 







US20060202194


 







US20070087321


 







US20080261076 US20100090591


 







US20070087321


 







Adv. Mater. 19, 739 (2007)


 







WO2009100991


 







WO20089101842


 







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


 


Platinum(II) organometallic  complexes




WO2003040257


 







US20070103060


 


Osminum(III)  complexes




Chem. Mater. 17, 3532 (2005)


 


Ruthenium(II)  complexes




Adv. Mater. 17, 1059 (2005)


 


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




US20050244673


 







Green dopants









Iridium(III)  organometallic complexes




Inorg. Chem. 40, 1704 (2001)


 



and its derivatives



 







US20020034656


 







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


 







US20090108737


 







WO2010028151


 







EP1841834B


 







US20060127696


 







US20090039776


 







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


 







US20100244004


 







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


 







Chem. Mater. 16, 2480 (2004)


 







US20070190359


 







US 20060008670 JP200723392


 







WO2010086089, WO2011044988


 







Adv. Mater. 16, 2003 (2004)


 







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


 







WO2009050290


 







US20090165846


 







US20080015355


 







US20010015432


 







US20100295032


 


Monomer for  polymeric  metal organo- metallic compounds




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


 


Pt(II) organo- metallic complexes,  including polydentated  ligands




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


 







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


 







Chem. Lett. 34, 592 (2005)


 







WO2002015645


 







US20060263635


 







US20060182992 US20070103060


 


Cu complexes




WO2009000673


 







US20070111026


 


Gold complexes




Chem. Commun. 2906 (2005)


 


Rhenium(III)  complexes




Inorg. Chem. 42, 1248 (2003)


 


Osmium(II)  complexes




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


 


Deuterated  organometallic complexes




US20030138657


 


Organometallic  complexes with two or  more metal centers




US20030152802


 







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


 







Blue dopants









Iridium(III)  organometallic complexes




WO2002002714


 







WO2006009024


 







US20060251923 US20110057559 US20010204333


 







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


 







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


 







WO2011051404


 







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


 







US20070190359, US20080297033 US20100148663


 







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


 







US20020134984


 







Angew. Chem. Int. Ed. 47, 1 (2008 )


 







Chem. Mater. 18, 5119 (2006)


 







Inorg. Chem. 46, 4308 (2007)


 







WO2005123873


 







WO2005123873


 







WO2007004380


 







WO2006082742


 


Osmium(II)  complexes




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


 







Organometallics 23, 3745 (2004)


 


Gold complexes




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


 


Platinum(II)  complexes




WO2006098120, WO2006103874


 


Pt tetradentate  complexes with at least  one metal- carbene bond




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


 







Exciton/hole blocking layer materials









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




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


 







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


 


Metal 8- hydroxy- quinolates (e.g., BAlq)




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


 


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




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


 


Triphenylene  compounds




US20050025993


 


Fluorinated  aromatic compounds




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


 


Phenothiazinc- S-oxide




WO2008132085


 


Silylatcd five- membered nitrogen,  oxygen, sulfur  or phosphorus dibenzo- heterocycles




WO2010079051


 


Aza-carbazoles




US20060121308


 







Electron transporting materials









Anthracene- benzoimidazole  compounds




WO2003060956


 







US20090179554


 


Aza  triphenylene derivatives




US20090115316


 


Anthracene- benzothiazole compounds




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


 


Metal 8- hydroxy- quinolates (e.g., Alq3, Zrq4)




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


 


Metal hydroxybeno- quinolates




Chem. Lett. 5, 905 (1993)


 


Bathocuprine  compounds such as BCP,  BPhen, etc




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


 







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


 


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




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


 







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


 







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


 


Silole  compounds




Org. Electron. 4, 113 (2003)


 


Arylborane  compounds




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


 


Fluorinatcd  aromatic compounds




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


 


Fullerene  (e.g., C60)




US20090101870


 


Triazine  complexes




US20040036077


 


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




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









EXPERIMENTAL
Calculation and Measurement of Decrease in LUMO Level
DFT calculations with the Gaussian software package at the B3LYP/cep-31g functional and basis set and cyclic voltammetry (CV) measurements in DMF solution with 0.1 M NBu4PF6 were carried out for two heteroleptic complexes of Formula (I) and two homoleptic complexes. TABLE 2 below shows the calculated values for the HOMO and the LUMO, and shows the respective oxidation and reduction values for the CV measurement. The CV measurements used ferrocene as a reference. The LUMO energies for the tris(cyclometallated) complexe Compound W and Compound X are closer to the vacuum level and therefore harder to reduce, with reduction potentials of −2.90 V and −3.10 V, respectively. It has been unexpectedly discovered that for the inventive compounds, the reduction potentials are further from the vacuum level and therefore the complexes are easier to reduce. To wit, Compound 59 has a reduction potential of −2.73 V (compared to −3.10 V in the comparative Compound X). Likewise, Compound 1 has a reduction potential of −2.75 V, compared to −2.90 V in the comparative Compound W. Without being bound by theory, it is believed that large negative reduction potentials can lead to instabilities in the OLED devices and the inability to trap charge well in the emissive layer. The inventive compounds presented here remove the instabilities associated with large reduction potentials and allow for better charge trapping in the emissive layer.
In addition, the HOMO energy levels for the inventive compounds are further from the vacuum level, making the compounds more difficult to oxidize. Compound 59 has an oxidation potential of 0.29 V while the comparative Compound X has an oxidation potential of 0.05 V. Likewise, Compound 1 has an oxidation potential of 0.41 V while the comparative Compound W has an oxidation potential of 0.20 V. Without being bound by theory, it is believed that small oxidation potentials can lead to instabilities due oxidative agents (e.g., oxygen) in the OLED devices and can lead to hole trapping exclusively by the emitting species, therefore reducing the emissive lifetime. The inventive compounds presented here remove the instabilities associated with small reduction potentials and allow for better charge trapping in the emissive layer.











TABLE 2





Structure
HOMO (eV)
LUMO (eV)
Ox. (V)
Red. (V)











−4.51
−1.13
0.29
−2.73


 






−4.59
−1.19
0.41
−2.75


 






−4.63
−1.03
0.20
−2.90


 






−4.42
−0.63
0.05
−3.10









Photoluminescence measurements further showed an unexpected advantage of incorporating a 6-membered metallocyclic ring into the complexes. As shown in FIG. 4 below, broadening and red-shifting of the photoluminescence spectra was observed in inventive complexes Compound 1 and Compound 59 when compared to comparative complex Compound X.
Table 3 below shows the numerical values from the photoluminescence spectrum. Compound 1 shows a 54 nm red shift from comparative Compound X, while Compound 59 shows a more pronounced red shift of 78 nm. In addition, Compound 1 exhibits a broad emission spectrum with Full-Width Half Maximum (FWHM) of 104 nm compared to comparative Compound X with FWHM of 72 nm, while inventive Compound 59 is further broadened to FWHM of 116 nm. Such a broadening of the photoluminescence spectrum is advantageous in certain emissive displays, such as the production of white light wherein broadband emission is desired.









TABLE 3






Emission Maximum
Full-Width Half Maximum


Compound
(nm)
(nm)

















Compound 1
524
104


Compound 59
548
116


Compound X
470
72









Photoluminescence (PL) spectra were recorded for each of Compounds 1, 59, and X. FIG. 4 shows the PL spectra for the three compounds superimposed onto the same graph. Compounds 1 and 59 show broader spectra compared to the homoleptic Compound X. Such broader PL spectra indicate that the compounds may be more beneficial for use in white light applications.
Compound Examples
Some of the heteroleptic complexes were synthesized as follows.
Synthesis of Compound 59
Synthesis of 2-(1-phenylethyl)pyridine




A 100 mL round-bottomed flask was charged with phenyllithium (1.8 M, 59 mL, 106 mmol) and cooled to 0° C. 2-Benzylpyridine (17.1 mL, 106 mmol) was dissolved in 55 mL ether and added dropwise to the reaction mixture over 30 min. at 0° C. The reaction mixture was stirred for 2.5 h at 0° C. before iodomethane (6.6 mL, 106 mmol) was added dropwise at 0° C. The reaction mixture was then stirred at room temperature for 16 h before being poured into cold saturated ammonium chloride solution and extracted by ethyl acetate. The organic portion was subjected to column chromatography (85:15 hexane:THF) to yield 18 g (92%) of 2-(1-phenyl-ethyl)pyridine.
Synthesis of 2-(2-phenylpropan-2-yl)pyridine




A 100 mL round-bottomed flask was charged with phenyllithium (1.8 M, 59 mL, 106 mmol) and cooled to 0° C. 2-(1-phenylethyl)pyridine (19.5 g, 106 mmol) was dissolved in 55 mL ether and added dropwise to the reaction mixture over 30 min. at 0° C. The reaction mixture was stirred for 2.5 h at 0° C. before iodomethane (6.6 mL, 106 mmol) was added dropwise at 0° C. The reaction mixture was then stirred at room temperature for 16 h before being poured into cold saturated ammonium chloride solution and extracted by ethyl acetate. The organic portion was subjected to column chromatography (85:15 hexane:THF) to yield 16 g (75%) of 2-(2-phenylpropan-2-yl)pyridine.
Synthesis of Compound 59




In a 50 mL round bottom flask was charged the iridium complex (0.5 g, 0.49 mmol) and 2-(2-phenylpropan-2-yl)pyridine (0.5 g, 2.5 mmol) and 8 drops of dichlorobenzene. The reaction mixture was heated to 200° C. for 21 h and, after cooling, subjected to column chromatography (80:20 hexane:THF) to 100 mg (20%) of Compound 59 as a yellow solid.
Synthesis of Compound 1




In a 50 mL round bottom flask was charged the iridium dimer complex (0.5 g, 0.24 mmol), silver(I) triflate (0.12 g, 0.48 mmol), DCM (10 mL) and methanol (10 mL). The reaction mixture was stirred for 3 h at room temperature, filtered and the filtrate evaporated to dryness. To the residue was added 2-(2-phenylpropan-2-yl)pyridine (0.32 g, 1.63 mmol) and 8 drops of dichlorobenzene. The reaction mixture was heated to 200° C. for 19 h and, after cooling, the crude mixture was subjected to column chromatography on silica gel (80:20 hexane:THF) to give 49 mg (16%) of Compound 1 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 of Formula (I):



wherein ring A and ring B are each independently a 5- or 6-membered carbocyclic or heterocyclic ring;
wherein L1 is BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, or GeRR′;
wherein Z1 and Z2 are independently carbon or nitrogen;
wherein at least one of Z1 and Z2 is carbon;
wherein





is a bidentate ligand selected from the group consisting of:







wherein R1, Ra, Rb, Re, and Rd may represent no substitution up to the maximum possible substitution;
wherein R1, R2, R, R′, R′a, Ra, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents of R1, R2, R, R′, Ra, Rb, Rc, and Rd are optionally joined to form a ring and can be further substituted; and
wherein n is 1 or 2.

2. The compound of claim 1, wherein

3. The compound of claim 1, wherein A-L1-B is

4. The compound of claim 3, wherein L1 is CRR′, wherein R and R′ are alkyl.

5. The compound of claim 4, wherein CRR′ is C(CH3)2.

6. The compound of claim 1, wherein A-L1-B is:



wherein R6 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.

7. The compound of claim 1, wherein A-L1-B is




wherein R5 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.

8. The compound of claim 1, wherein the ring A is an imidazole ring, which may be substituted as indicated, and Z1 is nitrogen.

9. The compound of claim 1, wherein A-L1-B is




wherein R5 and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

10. The compound of claim 1, wherein




is:




and wherein R7 and R8 are alkyl.

11. The compound of claim 1, which is selected from the group consisting of:

12. 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 of Formula (I):




wherein ring A and ring B are each independently a 5 or 6-membered carbocyclic or heterocyclic ring;
wherein L1 is BR, NR, PR, O, S, Se, C═O, S═O, SO2, CRR′, SiRR′, or GeRR′;
wherein Z1 and Z2 are independently carbon or nitrogen;
wherein at least one of Z1 and Z2 is carbon;
wherein





is a bidentate ligand selected from the group consisting of:



wherein R1, R2, R′a, Ra, Rb, Rc, and Rd may represent no substitution up to the maximum possible substitution;
wherein R1, R2, R, R′, Rb, Rc, and Rd are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof;
wherein any two adjacent substituents of R1, R2, R, R′, Ra, Rb, Rc, and Rd are optionally joined to form a ring and can be further substituted; and
wherein n is 1 or 2.

13. The first device of claim 12, wherein the first device is a consumer product.

14. The first device of claim 12, wherein the first device is an organic light-emitting device.

15. The first device of claim 12, wherein the first device comprises a lighting panel.

16. The first device of claim 12, wherein the organic layer is an emissive layer and the compound is an emissive dopant.

17. The first device of claim 12, wherein the organic layer is an emissive layer and the compound is a non-emissive dopant.

18. The first device of claim 12, wherein the organic layer further comprises a host.

19. The first device of claim 18, 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≡CCnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions;
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.

20. The first device of claim 18, wherein the host is selected from the group consisting of:







, and combinations thereof.

21. The first device of claim 18, wherein the host comprises a metal complex.

22. The first device of claim 18, wherein the host comprises at least one of the chemical groups selected from the group consisting of carbazole, dibenzothiophene dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.