# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

Novel heteroleptic iridium carbene complexes are provided, which contain phenyl imidazole moieties. In particular, ligands containing 2,4,6-trisubstituted N-phenyl imidazole fragments have highly desirable properties that make them suitable materials for use in OLED devices.

## Background
This application claims priority to U.S. application Ser. No. 61/494,667, filed Jun. 8, 2011, which is herein incorporated by reference in its entirety.


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 novel heteroleptic iridium carbene complexes. In particular, these iridium complexes are phosphorescent and are useful as emitters in OLED devices.
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 processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
SUMMARY OF THE INVENTION
A compound comprising a heteroleptic iridium complex having the formula:




Formula I, is provided. In the compound of Formula I, R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution, wherein R7 is selected from the group consisting of 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. R1, R3, R4, R5, R6, R8, R9, and R10 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. Each of R5 and R9 has a molecular weight more than 15.5 g/mol, any two adjacent substituents are optionally joined to form a ring and may be further substituted, and n is 1 or 2.

In one aspect, n is 2. In one aspect, n is 1. In one aspect, R5 and R9 are alkyl or cycloalkyl with at least two carbon atoms.
In one aspect, R5 and R9 are independently selected from the group consisting of: 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, and cyclohexyl, wherein each group is optionally partially or fully deuterated.
In one aspect, R5 and R9 are aryl or heteroaryl. In one aspect, R7 is aryl or heteroaryl. In one aspect, R7 is phenyl.
In one aspect, R1 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In one aspect, at least one of R1 to R10 contains deuterium.
In one aspect, the compound has the formula:




Formula II, wherein Y is selected from the group consisting of O, S, NR17, and CR12R13. R11 represents mono, di, tri, tetra substitutions or no substitution. R11, R12, R13 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.

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
















wherein X is O or S and Y is O or S. R5 and R9 are each independently selected from the group consisting of methyl-d3, 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, and combinations thereof; wherein each group is optionally partially or fully deuterated. R1 and R7 are each independently selected from 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.

In one aspect, the compound is selected from the group consisting of Compound 1-Compound 61.
In one aspect, a first device is provided. The first device comprises an 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:




Formula I, is provided. In the compound of Formula I, R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution, wherein R7 is selected from the group consisting of 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. R1, R3, R4, R5, R6, R8, R9, and R10 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. Each of R5 and R9 has a molecular weight more than 15.5 g/mol, any two adjacent substituents are optionally joined to form a ring and may be further substituted, and n is 1 or 2.

In one aspect, the organic layer is an emissive layer and the compound is an emissive dopant. In one aspect, the organic layer further comprises a host.
In one aspect, 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.
In one aspect, the host is a metal complex. In one aspect, the host is a metal carbene complex.
In one aspect, the metal carbene complex is selected from the group consisting of:



















In one aspect, the device further comprises a second organic layer that is a non-emissive layer between anode and the emissive layer; and wherein the material in the second organic layer is a metal carbene complex.
In one aspect, the device further comprises a third organic layer that is a non-emissive layer between cathode and the emissive layer; and wherein the material in the third organic layer is a metal carbene complex.
In one aspect, the device further comprises a second organic layer that is a non-emissive layer and the compound of Formula I is a material in the second organic layer.
In one aspect, the second organic layer is a hole transporting layer and the compound of Formula I is a transporting material in the second organic layer.
In one aspect, the second organic layer is a blocking layer and the compound having Formula I is a blocking material in the second organic layer.
In one aspect, the first device is an organic light-emitting device.
In one aspect, the first device is a consumer product.
In one aspect, the first device comprises a lighting panel.



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 compound of Formula I.



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 a 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-11”), 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, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
A compound comprising a heteroleptic iridium complex having the formula:




Formula I, is provided. In the compound of Formula I, R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution, wherein R7 is selected from the group consisting of 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. R1, R3, R4, R5, R6, R8, R9, and R10 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. Each of R5 and R9 has a molecular weight more than 15.5 g/mol, any two adjacent substituents are optionally joined to form a ring and may be further substituted, and n is 1 or 2.

In one embodiment, n is 2. In one embodiment, n is 1. In one embodiment, R5 and R9 are alkyl or cycloalkyl with at least two carbon atoms.
In one embodiment, R5 and R9 are independently selected from the group consisting of: 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, and cyclohexyl, wherein each group is optionally partially or fully deuterated.
In some embodiments, it is preferred that the both groups R5 and R9 are at least as large as an iso-propyl group. Such groups create a twist in the aryl ring to which they are attached to, which, without being bound by theory, is believed to provide more protection for the complex and thereby results in more stable devices when compounds of Formula I are used as emitters.
In one embodiment, R5 and R9 are aryl or heteroaryl. In one embodiment, R7 is aryl or heteroaryl. In one embodiment, R7 is phenyl.
In one embodiment, R1 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In one embodiment, at least one of R1 to R10 contains deuterium.
In one embodiment, the compound has the formula:




Formula II, wherein Y is selected from the group consisting of O, S, NR12, and CR12R13. R11 represents mono, di, tri, tetra substitutions or no substitution. R11, R12, R13 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.

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
















wherein X is O or S and Y is O or S. R5 and R9 are each independently selected from the group consisting of methyl-d3, 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, and combinations thereof; wherein each group is optionally partially or fully deuterated. R1 and R7 are each independently selected from 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.

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

















































In one embodiment, a first device is provided. The first device comprises an 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:




Formula I, is provided. In the compound of Formula I, R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution, wherein R7 is selected from the group consisting of 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. R1, R3, R4, R5, R6, R8, R9, and R10 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. Each of R5 and R9 has a molecular weight more than 15.5 g/mol, any two adjacent substituents are optionally joined to form a ring and may be further substituted, and n is 1 or 2.

In one embodiment, the organic layer is an emissive layer and the compound is an emissive dopant. In one embodiment, the organic layer further comprises a host.
In one embodiment, 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.
The “aza” designation in the fragments'described above, i.e. aza-dibenzofuran, aza-dibenzonethiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
In one embodiment, the host is a metal complex. In one embodiment, the host is a metal carbene complex. The term “metal carbene complex,” as used herein to refer to a metal coordination complex comprising at least one carbene ligand.
In one embodiment, the metal carbene complex is selected from the group consisting of:



















In one embodiment, the device further comprises a second organic layer that is a non-emissive layer between anode and the emissive layer; and wherein the material in the second organic layer is a metal carbene complex.
In one embodiment, the device further comprises a third organic layer that is a non-emissive layer between cathode and the emissive layer; and wherein the material in the third organic layer is a metal carbene complex.
In one embodiment, the device further comprises a second organic layer that is a non-emissive layer and the compound of Formula I is a material in the second organic layer.
In one embodiment, the second organic layer is a hole transporting layer and the compound of Formula I is a transporting material in the second organic layer.
In one embodiment, the second organic layer is a blocking layer and the compound having Formula I is a blocking material in the second organic layer.
In one embodiment, the first device is an organic light-emitting device.
In one embodiment, the first device is a consumer product.
In one embodiment, the first device comprises a lighting panel.
Device Data
All device examples were fabricated by high vacuum (<10−7 Torr) thermal evaporation (VTE). The anode electrode is 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1000 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 device examples consisted of sequentially, from the ITO surface, 100 Å of LG 101 (purchased from LG Chem) as the hole injection layer (HIL), 300 Å of 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) or 2% Alq (tris-8-hydroxyquinoline aluminum) doped NPD as the hole transporting layer (HTL), 300 Å of 15 wt % of a compound of Formula I doped in Compound H as the emissive layer (EML), 50 Å blocking layer (BL), 350 Å Alq as the electron transport layer (ETL). The device results and data are summarized in Table 1 and Table 2 from those devices. As used herein, NPD, Alq, Compound A, and Compound H have the following structures:











TABLE 1







VTE Phosphorescent OLEDs












Example
HIL
HTL
EML (300 Å, doping %)
BL
ETL
















Comparative
LG101 100 Å
NPD: 2% Alq
Compound H
Compound A
Compound H
Alq 350 Å


Example 1

300 Å

15%
50 Å


Example 1
LG101 100 Å
NPD: 2% Alq
Compound H
Compound 1
Compound H
Alq 350 Å




300 Å

15%
50 Å


Example 2
LG101 100 Å
NPD: 2% Alq
Compound H
Compound 17
Compound H
Alq 350 Å




300 Å

15%
50 Å
















TABLE 2







VTE Device Data at 1000 nits


















λmax
FWHM
Voltage
LE
EQE
LT80 %


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





Comparative
0.170
0.324
494
71
5.4
32.2
15.6
296


Example 1


Example 1
0.171
0.320
464
64
6.1
31.3
15.3
506


Example 2
0.159
0.281
464
54
5.7
26.8
14.4
184









Table 2 summarizes the device data. The luminous efficiency (LE) and external quantum efficiency (EQE) were measured at 1000 nits, while the lifetime (LT80%) was defined as the time required for the device to decay to 80% of its initial luminance of 1000 nits under a constant current density. Compound 1, a compound of Formula I, has phenyl substitution at the R7 position. This substitution improved device performance significantly compared to the Comparative Compound A. In devices containing 15% doping of the emissive compound (i.e. a compound of Formula I or a comparative example), both Compound 1 and Compound A showed similar color with a CIE of (0.17, 0.32) and similar EQE of about 15.5%. However, Compound 1 showed a LT80 of 506 hours, while Compound A had a LT80 of only 296 hours, which corresponds to a 70% improvement. Therefore, it is desirable to have the structure feature of the inventive compounds.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphryin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and sliane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:




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




k is an integer from 1 to 20; 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; (Y1-Y2) is a bidentate ligand, Y1 and Y2 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, (Y1-Y2) is a 2-phenylpyridine derivative.
In another aspect, (Y1-Y2) 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.
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:




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 is selected from C (including CH) or N.
Z1 and Z2 is selected from NR1, 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 0 to 20; L is an ancillary ligand, m 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:




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 3 below. Table 3 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.









TABLE 3





MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS















Hole injection materials









Phthalocyanine and porphryin compounds




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


 


Starburst tiarylamines




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


 



and



 










 










 


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^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 


 







US7232618


 


Platinum(II) organometallic complexes




WO2003040257 


 







US20070103060


 


Osminum(III) complexes 




Chem. Mater. 17,3532 (2005) 


 


Ruthenium(ll) complexes 




Adv. Mater. 17, 1059 (2005) 


 


Rhenium (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 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(Il) complexes 




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


 


Deuterated organometallic complexes 




US20030138657 


 


Organometallic complexes with two or more metal centers




US2003015802


 







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., triazoIe, 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
Chemical abbreviations used throughout this document are as follows: dba is dibenzylideneacetone, EtOAc is ethyl acetate, PPh3 is triphenylphosphine, dppf is 1,1′-bis(diphenylphosphino)ferrocene, DCM is dichloromethane, SPhos is dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-3-yl)phosphine, THF is tetrahydrofuran.
Synthesis
Synthesis of Compound 17
Step 1




A mixture solution of 4-iododibenzo[b,d]furan (18.4 g, 62.6 mmol), 1H-imidazole (5.11 g, 75 mmol), CuI (0.596 g, 3.13 mmol), Cs2CO3 (42.8 g, 131 mmol), cyclohexane-1,2-diamine (1.43 g, 12.51 mmol) in DMF (200 mL) was heated at 150° C. under nitrogen for 20 h. After cooling to room temperature, it was quenched with water and extracted with ethyl acetate. The combined extracts were washed with brine and filtered through a short plug of silica gel. Upon evaporation off the solvent, the crude product was dissolved in ethyl acetate and precipitated in hexane to yield 1-dibenzo[b,d]furan-4-yl)-1H-imidazole (12.2 g, 83%) as a white solid.
Step 2




A solution of 1-dibenzo[b,d]furan-4-yl)-1H-imidazole (10 g, 42.7 mmol) and iodomethane (30.3 g, 213 mmol) in ethyl acetate (100 mL) was stirred at room temperature for 24 h. The precipitate was isolated by filtration to yield 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazol-3-ium iodide (15.3 g, 93%) as a white solid.
Step 3




A mixture of 1-(dibenzo[b,d]furan-4-yl)-3-methyl-1H-imidazol-3-ium iodide (2.5 g, 6.65 mmol) and Ag2O (0.770 g, 3.32 mmol) in acetonitrile (150 mL) was stirred under nitrogen overnight. After evaporation of the solvent, the iridium phenylimidazole complex (2.58 g, 2.215 mmol) and THF (150 mL) was added. The resultant reaction mixture was refluxed under nitrogen overnight. After cooling to room temperature, it 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 triethylamine-treated silica gel with hexane/DCM (9/1 to 3/1, v/v) as eluent to yield the mer form of Compound 17 (1.9 g, 72%) as a green yellow solid.
Step 4




A solution of mer form of Compound 17 (1.9 g, 1.584 mmol) in anhydrous DMSO (100 mL) was irradiated with UV light under nitrogen for 3.5 h. Upon evaporation of the solvent, the residue was purified by column chromatography on triethylamine-treated silica gel with hexane/DCM (3/1, v/v) as eluent, followed by boiling in toluene to yield Compound 17 (1.2 g, 62%) as a green yellow solid.
Synthesis of Compound 1
Step 1




1-phenyl imidazole (6.8 g, 47.2 mmol) was dissolved in ethyl acetate (50 mL) in a 250 mL flask. To the mixture, MeI (33.5 g, 236 mmol) was added. The reaction mixture was stirring for 24 hours at room temperature. After filtration, a white salt (12.9 g, 96%) was obtained.
Step 2




The salt from step 1 (1.09 g, 3.8 mmol) and Ag2O (0.445 g, 1.9 mmol) and dry acetonitrile (150 mL) were charged in a 250 mL flask. The mixture was stirred overnight at room temperature, and the solvent was evaporated. To the residue, iridium dimer (2.5 g, 1.267 mmol) and 150 mL THF were added. The reaction mixture was then refluxed overnight. The mixture was cooled down and run through a Celite® bed with THF. Crude mer isomer (2.3 g, 82%) was obtained after evaporation of THF and washing with methanol.
Step 3




The mer isomer from Step 2 (2.0 g, 1.803 mmol) was dissolved in DMSO (150 mL) while heated in a photoreaction flask. The mixture was cooled down to room temperature. The solution was pumped and purged with N2 several times, and then irradiated with a UV lamp under N2 for 7 hours until HPLC showed the mer isomer was converted to the fac isomer. The product was purified by silica gel column chromatography with DCM in hexane as elute. Pure fac complex (1.0 g, 50%) was obtained after column. NMR and LC-MS both confirmed the desired product.
Synthesis of Compound 33
Step 1




4-Bromo-2,3-dihydro-1H-inden-1-one (9.5 g, 45.0 mmol) was added slowly to trifluoroacetic acid (TFA) (100 mL) at ice temperature. NaBH4 (8.51 g; 225 mmol) was added in potions. It was stirred in the ice bath for 1 hour and then allowed to warm up to room temperature. The reaction mixture was poured into an ice bath and the pH was adjusted to 8 with aq. NaOH. The mixture was extracted with DCM and dried on Na2SO4 and filtered. The organic mixture was purified by silica gel column chromatography (100% hexanes) to give 4-bromo-2,3-dihydro-1H-indene (4.9 g, 55%).
Step 2




A mixture of 4-bromo-2,3-dihydro-1H-indene (2.5 g, 12.7 mmol), imidazole (1.9 g, 28 mmol), CuI (0.5 g, 2.6 mmol), Cs2CO3 (8.7 g, 27 mmol), cyclohexane-1,2-diamine (0.29 g, 2.5 mmol) and DMF (50 mL) was purged with N2 and heated at 150° C. for two days. The reaction was cooled down and DCM was added. The organic layer was washed with water and then with aq. LiCl and dried on Na2SO4, filtered, concentrated, and then vacuum distilled at 190° C. (Kugelrohr) to give 1-(2,3-dihydro-1H-inden-4-yl)-1H-imidazole (2.0 g, 86.0%).
Step 3




To a solution of 1-(2,3-dihydro-1H-inden-4-yl)-1H-imidazole (2.0 g, 10.5 mmol) in ethyl acetate (40 mL) was added iodomethane (7.5 g, 53 mmol). The reaction was stirred overnight at room temperature. The resulting crystals were filtered off and wash with ethyl acetate. This gave the N-methyl iodide salt (2.7 g, 79%).
Step 4




A mixture of the N-methyl iodide salt (1.09 g, 3.34 mmol), Ag2O (0.39 g, 1.67 mmol) and anhydrous acetonitrile (90 mL) was purged with N2 and stirred at room temperature overnight. The reaction was concentrated to remove the acetonitrile. Iridium dimer (2.2 g, 1.11 mmol) was added along with THF (90 mL) and refluxed overnight. After cooling to room temperature, the mixture was filtered through Celite® and concentrated. The residue was chromatographed (TEA treated column) eluting with hexanes:DCM (1:1, v/v) to give mer isomer (2.9 g wet, 113%).




A solution of mer isomer (2.9 g, 1.9 mmol) in DMSO (250 mL) was irradiated with UV light under N2 for 9 hours. DMSO was removed under vacuum at 145° C. (Kugelrohr) and the residue was chromatographed (TEA treated silica column) with hexane:dichloromethane as eluent and further purified by dissolving in dichloromethane and isopropyl alcohol and concentrating to remove dichloromethane. The resulting crystals were filtered off and washed with isopropanol to give pure Compound 33 (0.55 g, 19%).
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 comprising a heteroleptic iridium complex having the formula:



wherein R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution;
wherein (a) R7 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, or (b) R7 is aryl or heteroaryl and is joined to R6 or R8 to form a ring, which may be further substituted;
wherein (a) R6 and R8 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, or (b) R6 and R8 are independently aryl or heteroaryl and joined to an adjacent substituent to form a ring, which may be further substituted;
wherein R1, R3, R4, R5, R9, and R10 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 each of R5 and R9 has a molecular weight more than 15.5 g/mol;
wherein any two adjacent substituents are optionally joined to form a ring and may be further substituted;
wherein n is 1 or 2.

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

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

4. The compound of claim 1, wherein R5 and R9 are alkyl or cycloalkyl with at least two carbon atoms.

5. The compound of claim 4, wherein R5 and R9 can be independently selected from the group consisting of: 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, and cyclohexyl, wherein each group is optionally partially or fully deuterated.

6. The compound of claim 1, wherein R5 and R9 are aryl or heteroaryl.

7. The compound of claim 1, wherein R7 is aryl or heteroaryl and is joined to R6 or R8 to form a ring, which may be further substituted.

8. The compound of claim 7, wherein R7 is phenyl and is joined to R6 or R8 to form a ring.

9. The compound of claim 1, wherein R1 is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

10. The compound of claim 1, wherein at least one of R1 to R10 contains deuterium.

11. The compound of claim 1, wherein the compound has the formula:



wherein Y is selected from the group consisting of O, S, NR12, and CR12R13;
wherein R11 represents mono, di, tri, tetra substitutions or no substitution; and
wherein R11, R12, R13 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, sulfnyl, sulfonyl, phosphino, and combinations thereof.

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















wherein X is O or S; Y is O or S;
wherein R5 and R9 are each independently selected from the group consisting of methyl-d3, 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, and combinations thereof; wherein each group is optionally partially or fully deuterated; and
wherein R1 and R7 are each independently selected from 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.

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

14. A first device comprising an 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 R3, R4, and R10 represent mono, di, tri, tetra substitutions or no substitution;
wherein (a) R7 is selected from the group consisting of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, or (b) R7 is aryl or heteroaryl and is joined to R6 or R8 to form a ring, which may be further substituted;
wherein (a) R6 and R8 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, or (b) R6 and R8 are independently aryl or heteroaryl and joined to an adjacent substituent to form a ring, which may be further substituted;
wherein R1, R3, R4, R5, R9, and R10 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 each of R5 and R9 has a molecular weight more than 15.5 g/mol;
wherein any two adjacent substituents are optionally joined to form a ring and may be further substituted;
wherein each of R5 and R9 has a molecular weight more than 15.5 g/mol;
wherein any two adjacent substituents are optionally joined to form a ring and may be further substituted;
wherein n is 1 or 2.

15. The first device of claim 14, wherein the organic layer is an emissive layer and the compound is an emissive dopant.

16. The first device of claim 14, wherein the organic layer further comprises a host.

17. The first device of claim 16, 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.

18. The first device of claim 16, wherein the host is a metal complex.

19. The first device of claim 18, wherein the host is a metal carbene complex.

20. The first device of claim 19, wherein the metal carbene complex is selected from the group consisting of:

21. The first device of claim 19, wherein the device further comprises a second organic layer that is a non-emissive layer between anode and the emissive layer; and wherein the material in the second organic layer is a metal carbene complex.

22. The first device of claim 21, wherein the device further comprises a third organic layer that is a non-emissive layer between cathode and the emissive layer; and wherein the material in the third organic layer is a metal carbene complex.

23. The first device of claim 14, wherein the device further comprises a second organic layer that is a non-emissive layer and the compound of Formula I is a material in the second organic layer.

24. The first device of claim 23, wherein the second organic layer is a hole transporting layer and the compound of Formula I is a transporting material in the second organic layer.

25. The first device of claim 23, wherein the second organic layer is a blocking layer and the compound having Formula I is a blocking material in the second organic layer.

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

27. The first device of claim 14, wherein the first device is a consumer product.

28. The first device of claim 14, wherein the first device comprises a lighting panel.