# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

A compound according to Formula I, as well as, devices and formulations containing the compound as described. The compound has the general formula




    
    
        wherein n=1 or 2; wherein X1-X2 is a bidentate ligand having the formula:
    
    






    
    
        wherein each of R1, R2, R3, R4 and R5 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;
        wherein each of R3, R4 and R5 can also be selected from two adjacent substituents joined to form into a ring;
        wherein each of Z1, Z2, Z3, Z4, Z6, Z7, Z8 is independently selected from C, CH or N;
        wherein ring A is connected to ring B through N—C bond; and
        wherein Y1-Y2 is a different bidentate ligand other than X1-X2.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Patent Application Ser. No. 61/649,463 filed May 21, 2012, the entire content of which is incorporated herein by reference.


PARTIES TO A JOINT RESEARCH AGREEMENT
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
FIELD OF THE INVENTION
The present invention relates to compounds for use as emitters and devices, such as organic light emitting diodes, including the same.
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
According to an embodiment, a compound is provided that has the structure of Formula I shown below




    
    
        wherein n=1 or 2;
        wherein X1-X2 is a bidentate ligand having the formula:
    
    






    
    
        wherein each of R1, R2 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;
        wherein R3, R4 and R5 may represent mono, di, tri, tetra substitutions, or no substitution;
        wherein each of R3, R4 and R5 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, and wherein two adjacent substituents are optionally joined to form into a ring;
        wherein each of Z1, Z2, Z3, Z4, Z6, Z7, Z8 is independently selected from C, CH or N;
        wherein ring A is connected to ring B through N—C bond; and
        wherein Y1-Y2 is a different bidentate ligand other than X1-X2.
    
    


According to another embodiment, a first device comprising a first organic light emitting device is also provided. The first device can include an anode, a cathode, and an organic layer, disposed between the anode and the cathode. The organic layer can include a compound of Formula I. The first device can be a consumer product, an organic light-emitting device, and/or a lighting panel.
According to still another embodiment, a formulation that includes a compound of Formula I is provided.



BRIEF DESCRIPTION OF THE DRAWINGS
The present disclosure is best understood from the following detailed description when read in conjunction with the accompanying drawing. It is emphasized that, according to common practice, the various features of the drawing are not necessarily to scale. On the contrary, the dimensions of the various features are arbitrarily expanded or reduced for clarity. Like numerals denote like features throughout the specification and 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 Formula I as disclosed herein.



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 proccessability 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, alkylaryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant carbon. Thus, where R4 is monosubstituted, then one R4 must be other than H. Similarly, where R4 is disubstituted, the two of R4 must be other than H. Similarly, where R4 is unsubstituted R4 is hydrogen for all available positions.
According to an embodiment, heteroleptic iridium complexes containing carbazole-imidazole-carbene ligands are provided. Metal carbene complexes have been developed as deep-blue emitters in phosphorescent OLEDs. However, devices based on these metal carbene complexes suffer from poor stability. This device instability is attributable to a number of possible factors, such as high sublimation temperature, slow triplet exciton decay, and unbalanced electron/hole fluxes in the device, etc. In this invention, carbene ligands are combined with other ligands to form metal complexes that modulate the HOMO/LUMO energy levels, emission spectra and charge transport properties, while promoting radiative decay of triplet excitons. These properties are further fine-tuned by introducing carbazole group attached to the imidazole-carbene moiety. Through this molecular design strategy, it is possible to integrate all desired merits of different ligands in one molecule. The device is also carefully designed so that it contains high triplet host, HTL, and/or HBL that will not quench the deep blue emitters.
The heteroleptic iridium complexes containing carbazole-imidazole-carbene ligands, which may be advantageously used in OLEDs, have the structure of Formula I:




wherein n=1 or 2;

wherein X1-X2 is a bidentate ligand having Formula II:





wherein each of R1, R2 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. R3, R4 and R5 may represent mono, di, tri, tetra substitutions, or no substitution. Each of R3, R4 and R5 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, and wherein two adjacent substituents are optionally joined to form into a ring. Each of Z1, Z2, Z3, Z4, Z6, Z7, Z8 is independently selected from C, CH or N; ring A is connected to ring B through N—C bond; and Y1-Y2 is a different bidentate ligand other than X1-X2.

In some embodiments, X1-X2 can be selected from the group consisting of




In some embodiments, Y1-Y2 can be selected from the group consisting of:




wherein Ra Rb Rc Rd are selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein two adjacent substituents are optionally joined to form into a ring.

More specifically, in some embodiments, Y1-Y2 can be:




wherein Rg represents mono, di, tri, substitutions or no substitution. Re, Rf, and Rg 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. At least one of Re and Rf is not hydrogen or deuterium.

In some embodiments, neither Re nor Rf is hydrogen or deuterium. In some embodiments, ring B is coupled to the central Ir atom of Formula I through an Ir—C bond. In other words, the one of Z1-Z4 that is coupled to the central Ir atom is C.
In some embodiments, R1 can be selected from the group consisting of deuterium, linear, branched or cyclic C1-C8 alkyl, aryl, alkylaryl, heteroaryl and combinations thereof. More specifically, in some embodiments, R1 can be 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, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof; and wherein each group is optionally partially or fully deuterated.
Examples of C1-C8 alkyl that can be useful in the formulas herein, include 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, and combinations thereof; wherein each group is optionally partially or fully deuterated. Examples of aryl or alkyaryl that can be useful in the formulas herein include phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof; and wherein each group is optionally partially or fully deuterated.
In some embodiments, R2 can be selected from the group consisting of deuterium, linear, branched or cyclic C1-C8 alkyl, aryl, alkylaryl, heteroaryl and combinations thereof. More specifically, in some embodiments, R2 can be selected from the group consisting of substituted or unsubstituted benzene and pyridine. The benzene or pyridine can be substituted by deuterium, C1-C8 alkyl, C6-C30 aryl, C5-C30 heteroaryl, and combinations thereof.
In some embodiments, R3 is disubstituted and R3 comprises two adjacent substituents joined to form an aryl, alkylaryl or heteroaryl ring. In some more specific embodiments, ring A can have the structure selected from the group consisting of:




In some embodiments, R4 can be mono, di or trisubstituted, and at least one R4 is selected from the group consisting of C1-C8-alkyl.
In some embodiments, R5 is disubstituted, and R5 comprises two adjacent substituents joined to form an aryl, alkylaryl or heteroaryl ring.
In some embodiments, at least one of Z1-Z4 is N, or at least two of Z1-Z4 are N, or at least three of Z1-Z4 are N. In some embodiment, one of Z1-Z4 is N. In other embodiments, two of Z1-Z4 are N, or three of Z1-Z4 are N. In still other embodiments, each of Z1-Z4 is N.
In some embodiments, at least one of Z5-Z8 is N, or at least two of Z5-Z8 are N, or at least three of Z5-Z8 are N. In some embodiment, one of Z5-Z8 is N. In other embodiments, two of Z5-Z8 are N, or three of Z5-Z8 are N. In still other embodiments, each of Z5-Z8 is N.
In some more specific embodiments, X1-X2 can be selected from the group consisting of:




























In other more specific embodiments, Y1-Y2 can be selected from the following:




























In some embodiments, n can be 1, while n can be 2 in other embodiments.

In some embodiments, the compound can be selected from the group consisting of:





































According to another aspect of the present disclosure, a first device is also provided. The first device includes a first organic light emitting device, that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer can include a compound according to Formula I, and its variations as described herein.
The first device can be one or more of a consumer product, an organic light-emitting device and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
The organic layer can also include a host. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1-Ar2, CnH2n—Ar1, or no substitution. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
The host can be a compound 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. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:










and combinations thereof.

In yet another aspect of the present disclosure, a formulation that includes a compound according to Formula I is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, an electron transport layer material (see below).
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 silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:




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




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, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k′′ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:




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




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

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







R101 to R107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
k is an integer from 0 to 20 or 1 to 20; k′′′ is an integer from 0 to 20.
X101 to X108 is selected from C (including CH) or N.
Z101 and Z102 is selected from NR101, O, or S.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:




k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:




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, 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 (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)


 


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




Org. Electron. 1, 15 (2000)


 


Aromatic fused rings




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


 


Zinc complexes




WO2010056066


 


Chrysene based compounds




WO2011086863


 







Green hosts









Arylcarbazoles




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


 







US20030175553


 







WO2001039234


 


Aryltriphenylene compounds




US20060280965


 







US20060280965


 







WO2009021126


 


Poly-fused heteroaryl compounds




US20090309488 US20090302743 US20100012931


 


Donor acceptor type molecules




WO2008056746


 







WO2010107244


 


Aza-carbazole/ DBT/DBF




JP2008074939


 







US20100187984


 


Polymers (e.g., PVK)




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


 


Spirofluorene compounds




WO2004093207


 


Metal phenoxybenzooxazole compounds




WO2005089025


 







WO2006132173


 







JP200511610


 


Spirofluorene- carbazole compounds




JP2007254297


 







JP2007254297


 


Indolocabazoles




WO2007063796


 







WO2007063754


 


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




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


 







WO2004107822


 


Tetraphenylene complexes




US20050112407


 


Metal phenoxypyridine compounds




WO2005030900


 


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




US20040137268, US20040137267


 







Blue hosts









Arylcarbazoles




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


 







US20070190359


 


Dibenzothiophene/ Dibenzofuran- carbazole compounds




WO2006114966, US20090167162


 







US20090167162


 







WO2009086028


 







US20090030202, US20090017330


 







US20100084966


 


Silicon aryl compounds




US20050238919


 







WO2009003898


 


Silicon/ Germanium aryl compounds




EP2034538A


 


Aryl benzoyl ester




WO2006100298


 


Carbazole linked by non-conjugated groups




US20040115476


 


Aza-carbazoles




US20060121308


 


High triplet metal organometallic complex




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


 







Phosphorescent dopants


Red dopants









Heavy metal porphyrins (e.g., PtOEP)




Nature 395, 151 (1998)


 


Iridium(III) organometallic complexes




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


 







US2006835469


 







US2006835469


 







US20060202194


 







US20060202194


 







US20070087321


 







US20080261076 US20100090591


 







US20070087321


 







Adv. Mater. 19, 739 (2007)


 







WO2009100991


 







WO2008101842


 







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


 


Platinum(II) organometallic complexes




WO2003040257


 







US20070103060


 


Osminum(III) complexes




Chem. Mater. 17, 3532 (2005)


 


Ruthenium(II) complexes




Adv. Mater. 17, 1059 (2005)


 


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




US20050244673


 







Green dopans









Iridium(III) organometallic complexes



   and its derivatives
Inorg. Chem. 40, 1704 (2001)


 







US20020034656


 







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


 







US20090108737


 







WO2010028151


 







EP1841834B


 







US20060127696


 







US20090039776


 







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


 







US20100244004


 







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


 







Chem. Mater. 16, 2480 (2004)


 







US20070190359


 







US20060008670 JP2007123392


 







WO2010086089, WO2011044988


 







Adv. Mater. 16, 2003 (2004)


 







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


 







WO2009050290


 







US20090165846


 







US20080015355


 







US20010015432


 







US20100295032


 


Monomer for polymeric metal organometallic compounds




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


 


Pt(II) organometallic complexes, including polydentated ligands




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


 







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


 







Chem. Lett. 34, 592 (2005)


 







WO2002015645


 







US20060263635


 







US20060182992 US20070103060


 


Cu complexes




WO2009000673


 







US20070111026


 


Gold complexes




Chem. Commun. 2906 (2005)


 


Rhenium(III) complexes




Inorg. Chem. 42, 1248 (2003)


 


Osmium(II) complexes




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


 


Deuterated organometallic complexes




US20030138657


 


Organometallic complexes with two or more metal centers




US20030152802


 







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


 







Blue dopants









Iridium(III) organometallic complexes




WO2002002714


 







WO2006009024


 







US20060251923 US20110057559 US20110204333


 







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


 







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


 







WO2011051404


 







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


 







US20070190359, US20080297033 US20100148663


 







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


 







US20020134984


 







Angew. Chem. Int. Ed. 47, 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-hydroxyquinolates (e.g., BAlq)




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


 


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




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


 


Triphenylene compounds




US20050025993


 


Fluorinated aromatic compounds




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


 


Phenothiazine- S-oxide




WO2008132085


 


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




WO2010079051


 


Aza-carbazoles




US20060121308


 







Electron transporting materials









Anthracene- benzoimidazole compounds




WO2003060956


 







US20090179554


 


Aza triphenylene derivatives




US20090115316


 


Anthracene- benzothiazole compounds




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


 


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




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


 


Metal hydroxybenoquinolates




Chem. Lett. 5, 905 (1993)


 


Bathocuprine compounds such as BCP, BPhen, etc




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


 







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


 


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




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


 







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


 







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


 


Silole compounds




Org. Electron. 4, 113 (2003)


 


Arylborane compounds




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


 


Fluorinated aromatic compounds




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


 


Fullerene (e.g., C60)




US20090101870


 


Triazine complexes




US20040036077


 


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




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









EXPERIMENTAL
Synthesis of Compound 1
A mixture solution of 2-bromo-9H-carbazole (10.0 g, 40.6 mmol), iodobenzene (12.43 g, 61.0 mmol), CuI (0.774 g, 4.06 mmol), (1R,2S)-cyclohexane-1,2-diamine (0.987 ml, 8.13 mmol), and K3PO4 (17.25 g, 81 mmol) in dioxane (150 ml) was refluxed under nitrogen for 48 h.




After cooling to room temperature, the mixture was filtered through a plug of Celite® and the solid was washed with DCM. The combined filtrate was evaporated and purified by column chromatography on silica gel with hexane/DCM (9/1, v/v) as eluent to yield 2-bromo-9-phenyl-9H-carbazole (7.4 g, 54%) as a white solid.




A mixture of 2-bromo-9-phenyl-9H-carbazole (11.6 g, 36.0 mmol), imidazole (3.68 g, 54.0 mmol), CuI (1.371 g, 7.20 mmol) and K2CO3 (7.46 g, 54.0 mmol) in DMF (150 ml) was heated under nitrogen at 140° C. overnight. After cooling to room temperature, the mixture was quenched with water and extracted with DCM. The combined extracts were filtered through a short plug of Celite®. The filtrate was washed with water and dried over Na2SO4. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with DCM/MeOH (10/0 to 95/5, v/v) as eluent to yield 2-(1H-imidazol-1-yl)-9-phenyl-9H-carbazole (11.1 g, 99%) as a liquid.




A solution of 2-(1H-imidazol-1-yl)-9-phenyl-9H-carbazole (3.5 g, 11.31 mmol) and iodomethane (3.52 ml, 56.6 mmol) in EtOAc (100 ml) was stirred at room temperature for 48 hours. The white precipitate was collected by filtration, washed with EtOAc and recrystallized from ethanol to yield 1-iodo-1-methyl-3-(9-phenyl-9H-carbazol-2-yl)-2,3-dihydro-1H-imidazol-1-ium-2-ide (3.5 g, 68%) as white crystals.




A solution of 1-iodo-1-methyl-3-(9-phenyl-9H-carbazol-2-yl)-2,3-dihydro-1H-imidazol-1-ium-2-ide (2.5 g, 5.54 mmol) and Ag2O (0.642 g, 2.77 mmol) in acetonitrile (150 ml) was stirred under nitrogen at room temperature overnight to yield a white suspension. The acetonitrile was evaporated off, and the residue was re-dissolved together with Ir-dimer (2 g, 1.198 mmol) in THF (150 ml). The resultant solution was refluxed under nitrogen overnight. After cooling to room temperature, the solution was filtered through a short plug of Celite® and washed with DCM. Upon evaporation of the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 4/1, v/v) as eluent to yield the mer form of the Compound 1 (2.3 g, 83%) as yellow crystals.




A solution of mer form of Compound 1 (2 g, 1.782 mmol) in DMSO (400 ml) was irradiated (360 nm) with UV light under nitrogen for 4 h. Upon evaporation of the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 4/1, v/v) as eluent to yield Compound 1 (1.4 g, 70%) as yellow crystals.




Synthesis of Compound 2
A mixture solution of 3-bromo-9-phenyl-9H-carbazole (7.9 g, 24.52 mmol), 1H-imidazole (2.504 g, 36.8 mmol), CuI (1.401 g, 7.36 mmol) and K2CO3 (5.08 g, 36.8 mmol) in DMF (100 ml) was heated at 140° C. under nitrogen overnight.




After cooling to room temperature, the mixture solution was filtered through a short plug of Celite®. The filtrate was poured into water, extracted with DCM and dried over Na2SO4. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with DCM/EtOAc (4/1, v/v) as eluent to yield 3-(1H-imidazol-1-yl)-9-phenyl-9H-carbazole (7 g, 92%) as a white powder.




A solution of 3-(1H-imidazol-1-yl)-9-phenyl-9H-carbazole (3.5 g, 11.31 mmol) and and iodomethane (3.52 ml, 56.6 mmol) in EtOAc (Volume: 100 ml) was stirred at room temperature for 72 h. The white precipitate was collected by filtration, washed with EtOAc and recrystallized from ethanol to yield 1-iodo-1-methyl-3-(9-phenyl-9H-carbazol-3-yl)-2,3-dihydro-1H-imidazol-1-ium-2-ide (3.4 g, 67%) as white crystals.




A mixture of 1-iodo-1-methyl-3-(9-phenyl-9H-carbazol-3-yl)-2,3-dihydro-1H-imidazol-1-ium-2-ide (2.5 g, 5.54 mmol) and Ag2O (0.642 g, 2.77 mmol) in acetonitrile (150 ml) was stirred under nitrogen at room temperature overnight. The acetonitrile was evaporated under reduced pressure. The solid was re-dissolved together with Ir-dimer (2 g, 1.20 mml) in THF (150 ml) and refluxed under nitrogen overnight. After cooling to room temperature, the reaction mixture was filtered through a short plug of Celite® and the filtrate was evaporated. The residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 3/1, v/v) as eluent to yield the mer-form of Compound 2 (2.3 g, 85%) as yellow crystals.




A solution of mer-form of Compound 2 (2.3 g, 2.049 mmol) in DMSO (200 ml) was irradiated (360 nm) with UV light under nitrogen for 3 h. Upon evaporation of the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (9/1 to 4/1, v/v) as eluent to yield fac-form of Compound 2 (1.6 g, 70%) as yellow crystals.




Synthesis of Compound 5
Into a suspension of 9H-pyrido[2,3-b]indole (8 g, 47.6 mmol) in DCM (350 ml) was added dropwise a solution of bromine (2.92 ml, 57.1 mmol) in DCM (60 ml) at room temperature during a period of 4 h.




The reaction mixture was stirred at room temperature overnight, quenched with an aqueous solution of Na2S2O3. The solid was isolated by filtration. The filtrate was washed with water and evaporated to obtain another solid. The combined solids were recrystallized from EtOAc to yield 6-bromo-9H-pyrido[2,3-b]indole (9.0 g, 77%) as white crystals.




A solution of 6-bromo-9H-pyrido[2,3-b]indole (4.42 g, 17.89 mmol), iodobenzene (2.94 ml, 26.8 mmol), CuI (3.41 g, 17.89 mmol), cyclohexane-1,2-diamine (0.435 ml, 3.58 mmol) and K3PO4 (7.59 g, 35.8 mmol) in xylene (250 ml) was refluxed overnight. After cooling to room temperature, the solution was filtered through a short plug of Celite® and the solid was washed with DCM. The combined filtrates were evaporated and the residue was purified by column chromatography on silica gel with DCM as eluent to yield 6-iodo-9-phenyl-9H-pyrido[2,3-b]indole (1.4 g, 21%) as a white solid.




A mixture solution of 6-iodo-9-phenyl-9H-pyrido[2,3-b]indole (1.15 g, 3.11 mmol), 1H-imidazole (0.32, 4.66 mmol), CuI (0.12 g, 0.62 mmol), cyclohexane-1,2-diamine (0.15 ml, 1.24 mmol) and K2CO3 (0.64 g, 4.63 mmol) in DMF (40 ml) was heated at 140° C. overnight. After cooling to room temperature, the mixture solution was poured into water (50 ml) and extracted with DCM. The combined extracts were washed with brine, dried over Na2SO4 and evaporated. The residue was purified by column chromatography on silica gel with DCM/EtOAc (3/1, v/v) as eluent to yield 6-(1H-imidazol-1-yl)-9-phenyl-9H-pyrido[2,3-b]indole (0.6 g, 62%) as a white solid.




A solution of 6-(1H-imidazol-1-yl)-9-phenyl-9H-pyrido[2,3-b]indole (0.6 g, 1.933 mmol) and iodomethane (0.60 ml, 9.67 mmol) in EtOAc (200 ml) was stirred at room temperature for 60 h. The precipitate was isolated and washed with EtOAc to yield 3-methyl-1-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)-1H-imidazol-3-ium iodide (0.48 g, 55%) as a white solid.




A suspension of 3-methyl-1-(9-phenyl-9H-pyrido[2,3-b]indol-6-yl)-1H-imidazol-3-ium iodide (0.48 g, 1.061 mmol) and Ag2O (0.123 g, 0.531 mmol) in acetonitrile (50 ml) was stirred under nitrogen at room temperature overnight. The solvent was evaporated, and the residue was refluxed overnight under nitrogen together with the Ir-dimer (0.59 g, 0.35 mmol) in THF (50 ml). The solid was filtered off and the residue was purified by column chromatography on TEA-treated silica gel with hexane/DCM (4/1, v/v) as eluent to yield mer-form of Compound 5 (0.3 g, 38%) as a yellow solid.




A solution of mer-form of Compound 5 (0.3 g, 0.267 mmol) in DMSO (50 ml) was irradiated with UV for 4 h. Upon evaporation off the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (4/1 to 2/1, v/v) as eluent to yield fac-form of Compound 5 as yellow crystals.




Computational Results
The HOMO/LUMO energy levels and triplet energy (T1) of selected compounds were calculated using the Gaussian software package at the B3LYP/cep-31g functional and basis set, and the results are presented in Table 2. Some of the heteroleptic iridium complexes described herein were compared with similar heteroleptic iridium complexes: comparative compound 1 (CC-1) and comparative compound 2 (CC-2):




Compared to homoleptic compound CC-1, the heteroleptic Compound 2 has higher triplet energy, 2.73 eV vs 2.67 eV, suggesting that the carbazole-imidazole-carbene ligand could effectively blue-shift the emission spectra. Furthermore, compared to homoleptic compound CC-2, the heteroleptic Compound 2 has elevated HOMO level, −4.46 eV vs −4.66 eV, which is attributable to the introduction of phenylimidzole ligand in Compound 2. A shallower HOMO level facilitates hole trapping and promotes charge recombination in the emitting layer, both of which are desirable for efficient and stable devices. In essence, the heteroleptic structures enable modulation of HOMO/LUMO levels, emission spectra and charge transport properties, and thus offers the opportunity to develop efficient and long-lasting phosphorescent OLEDs with blue emission.












TABLE 2







Compound
HOMO (eV)
LUMO (eV)
T1 (eV)









CC-1
−4.42
−0.63
2.67



CC-2
−4.66
−0.51
2.81



Compound 2
−4.46
−0.68
2.73










Device Examples
The structures of the materials used in the device examples are shown below:




All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation (VTE). The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices were 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 OLED device used in the Examples and Comparative Device Examples had the following structure: from the ITO surface, 100 Å of LG101 (purchased from LG Chem.) as the hole injection layer, 300 Å of NPD as the hole transporting layer (HTL), 300 Å of Compound DBT2Cz doped with 15 weight percent of a compound of Formula I or comparative compound CC-2 as the emissive layer (EML), 50 Å of compound DBT2Cz as the blocking layer (BL), and 400 Å of Alq as the electron transporting layer (ETL).
Table 3 is a summary of the device data. The driving voltage (V), luminous efficiency (LE) and external quantum efficiency (EQE) were measured at 1000 nits, while the lifetime (LT8O%) was defined as the time required for the device to decay to 80% of its initial luminance under a constant current density of 20 mA/cm2. The electroluminescence spectra of the devices are consistent with the trend of the calculated triplet energies of emitters, i.e. emitters with higher triplet energies exhibit electroluminescent spectra peaked at shorter wavelength. This suggests that the heteroleptic chemical structure described herein could effectively adjust the emission color of final compounds. On the other hand, compared to device (Device CC-2) with homoleptic compound CC-2 as the emitter, devices (Devices 1 and 2) with compounds of Formula I (Compounds 1 and 2) as emitters require less driving voltage while achieving significantly enhanced efficiency and lifetime. This improvement in device performance is attributable to the more desirable energy levels and charge transport properties derived from the heteroleptic compounds of Formula I.













TABLE 3













At 20


Device




At 1000 nits
mA/cm2















Exam-

λmax
CIE
CIE
V
LE
EQE
Relative


ples
Emitter
(nm)
x
y
(V)
(cd/A)
(%)
LT80%


















Device
Com-
472
0.165
0.318
5.7
14.9
7.5
17


1
pound 1


Device
Com-
464
0.167
0.292
5.4
21.7
11.2
17


2
pound 2


Device
CC-2
450
0.177
0.352
9.7
1.0
0.8
1


CC-2









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 the formula:



wherein n=1 or 2;
wherein X1-X2 is a bidentate ligand having the formula:




wherein each of R1, R2 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;
wherein R3, R4 and R5 may represent mono, di, tri, tetra substitutions, or no substitution;
wherein each of R3, R4 and R5 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, sulfonyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents are optionally joined to form into a ring;
wherein each of Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 is independently selected from C, CH or N;
wherein at least one of Z1-Z4 is N;
wherein ring A is connected to ring B through N—C bond; and
wherein Y1-Y2 is a different bidentate ligand other than X1-X2.

2. The compound of claim 1, wherein X1-X2 is selected from the group consisting of

3. The compound of claim 1, wherein Y1-Y2 is selected from the group consisting of



wherein Ra Rb Rc Rd are selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, wherein two adjacent substituents are optionally joined to form into a ring.

4. The compound of claim 3, wherein Y1-Y2 is



wherein Rg represents mono, di, tri, substitutions or no substitution;
wherein Re, Rf, and Rg are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein at least one of Re and Rf is not hydrogen or deuterium.

5. The compound of claim 1, wherein ring B is coupled to the central Ir atom of Formula I through an Ir—C bond.

6. The compound of claim 1, wherein R1 is selected from the group consisting of deuterium, linear, branched or cyclic C1-C8 alkyl, aryl, alkylaryl, heteroaryl and combinations thereof.

7. The compound of claim 6, wherein R1 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, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof; and wherein each group is optionally partially or fully deuterated.

8. The compound of claim 1, wherein R2 is selected from the group consisting of deuterium, linear, branched or cyclic C1-C8 alkyl, aryl, alkylaryl, heteroaryl and combinations thereof.

9. The compound of claim 8, wherein R2 is selected from the group consisting of substituted or unsubstituted benzene and pyridine.

10. The compound of claim 9, wherein R3 is disubstituted and R3 comprises two adjacent substituents joined to form an aryl, alkylaryl or heteroaryl ring.

11. The compound of claim 10, wherein ring A has the structure selected from the group consisting of:

12. The compound of claim 10, wherein ring A has the structure selected from the group consisting of:

13. The compound of claim 1, wherein R3 is disubstituted and R3 comprises two adjacent substituents joined to form an aryl, alkylaryl or heteroaryl ring.

14. The compound of claim 13, wherein ring A has the structure selected from the group consisting of:

15. The compound of claim 1, wherein R5 is disubstituted, and R5 comprises two adjacent substituents joined to form an aryl, alkylaryl or heteroaryl ring.

16. The compound of claim 1, wherein one of Z1-Z4 is N.

17. The compound of claim 1, wherein at least one of Z5-Z8 is N.

18. The compound of claim 1, wherein one of Z5-Z8 is N.

19. The compound of claim 1, wherein Y1-Y2 is

20. The compound of claim 1, wherein n=1.

21. The compound of claim 1, wherein n=2.

22. The compound of claim 1, wherein X1-X2 is selected from the group consisting of

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

24. The compound of claim 1, wherein ring A is connected to ring B through Z1 and Ring B is connected to the iridium atom by Z2.

25. 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:




wherein n=1 or 2;
wherein X1-X2 is a bidentate ligand having the formula:




wherein each of R1, R2 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;
wherein R3, R4 and R5 may represent mono, di, tri, tetra substitutions, or no substitution;
wherein each of R3, R4 and R5 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, sulfanyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents are optionally joined to form into a ring;
wherein each of Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 is independently selected from C, CH or N;
wherein at least one of Z1-Z4 is N;
wherein ring A is connected to ring B through N—C bond; and
wherein Y1-Y2 is a different bidentate ligand other than X1-X2.

26. The first device of claim 25, wherein the first device comprises a device selected from the group consisting of a consumer product, an organic light-emitting device, and a lighting panel.

27. The first device of claim 25, wherein the organic layer is an emissive layer and the compound is an emissive dopant.

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

29. The first device of claim 25, wherein the organic layer further comprises a host.

30. The first device of claim 29, 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 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.

31. The first device of claim 29, wherein the host comprises a compound selected from the group consisting of: carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

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









and combinations thereof.

33. The first device of claim 29, wherein the host comprises a metal complex.