# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

A novel type of blue emitter is described based on the azaphenanthridine imidazole ligand. The preferred use of this moiety for generating blue phosphorescence is as part of a symmetric platinum tetradentate complex.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from U.S. Provisional Patent Application Ser. Nos. 61/979,103, filed Apr. 14, 2014, and 61/991,720, filed May 12, 2014, the entire contents of each 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.
In some bis-bidentate and symmetric tetradentate imidazole phenanthridine platinum complexes, the emission energy is not blue enough for display and lighting applications. Furthermore, the uncoordinated nitrogen in the phenanthridine ring system presents a stability issue as it may be susceptible to protonation in the excited state. There is a need in the art for novel compounds with strong blue-shifting effects that are not susceptible to protonation of the uncoordinated nitrogen. The present invention addresses this unmet need.
SUMMARY OF THE INVENTION
According to an embodiment, a compound is provided having the formula:




wherein A and B are independently selected from the group consisting of a 5-membered or 6-membered carbocyclic or heterocyclic ring;
wherein one of A and B is an anionic coordinating atom, and the other of A and B is a neutral coordinating atoms;

    
    
        wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
    
    


wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R1, R2, R3, R′, and R′′ 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 any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.
In one embodiment, M is Pt.
In one embodiment, the compound has the formula:




In one embodiment, the compound has the formula:




wherein R 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.
In one embodiment, R is selected from the group consisting of alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof. In another embodiment, R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof.
In one embodiment, only one of X and Y is present.
In one embodiment, the compound is selected from the group consisting of:




wherein R6 represents mono, di, tri, or tetra-substitution, or no substitution;
wherein R4, R5, and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein any adjacent R4, R5, and R6 are optionally joined to form a ring.
In one embodiment, A-B is selected from the group consisting of:










wherein each X1 to X13 are independently selected from the group consisting of carbon and nitrogen;
wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, SiR′R′′, and GeR′R′′;
wherein R′ and R′′ are optionally fused or joined to form a ring;
wherein each Ra, Rb, Rc, and Rd may represent from mono substitution to the possible maximum number of substitution, or no substitution;
wherein RL represents mono substitution, or no substitution;
wherein Ra, Rb, Rc, Rd and RL 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 when Ra, Rb, Rc, and Rd represent at least di substitution, each of the two adjacent Ra, two adjacent Rb, two adjacent Rc, and two adjacent Rd are optionally fused or joined to form a ring;
wherein RL is optionally a linker to function as X or Y; and
wherein when X1 to X13 are used to link to X or Y, that X1 to X13 is carbon.
In one embodiment, the compound is selected from the group consisting of:














































According to another embodiment, a first device comprising a first organic light emitting device is also provided. The first organic light emitting 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.
In one embodiment, the first device comprises a first organic light emitting device, the first organic light emitting device comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, comprising a compound having the formula:




wherein A and B are independently selected from the group consisting of a 5-membered or 6-membered carbocyclic or heterocyclic ring;
wherein one of A and B is an anionic coordinating atom, and the other of A and B is a neutral coordinating atoms;
wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R1, R2, R3, R′, and R′′ 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 any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.
In one embodiment, the first device is selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel. In another embodiment, the organic layer is an emissive layer and the compound is an emissive dopant or a non-emissive dopant. In another embodiment, the organic layer is a charge transporting layer and the compound is a charge transporting material in the organic layer. In another embodiment, the organic layer is a blocking layer and the compound is a blocking material in the organic layer.
In one embodiment, the organic layer further comprises a host; 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 CnH2+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1—Ar2, CnHn2—Ar1, or no substitution;
wherein n is from 1 to 10; and
wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In one embodiment, the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
In one embodiment, the organic layer further comprises a host and the host is selected from the group consisting of:













and combinations thereof.

In one embodiment, the organic layer further comprises a host and the host comprises a metal complex.
According to another embodiment, a formulation comprising the above compound is also provided. In one embodiment, the formulation comprises a compound having the formula:




wherein A and B are independently selected from the group consisting of a 5-membered or 6-membered carbocyclic or heterocyclic ring;
wherein one of A and B is an anionic coordinating atom, and the other of A and B is a neutral coordinating atoms;
wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R1, R2, R3, R′, and R′′ 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 any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.



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 an emission spectrum of Comparative Example 1 measured at 77 K in 2-methyltetrahydrofuran solvent.
FIG. 4 shows an emission spectra of Comparative Example 2 in solid state PMMA matrix and 77 K and Room Temperature 2-methyltetrahydrofuran solvent.
FIG. 5 shows an emission spectra of Comparative Example 3 in 77 K and Room Temperature 2-methyltetrahydrofuran solvent.
FIG. 6 shows spectral data for Comparative Example 5 in 77 K 2-methyltetrahydrofuran solvent.



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 which is incorporated by reference in its entirety.
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 which is incorporated by reference in its entirety.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processibility than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.
The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alkyl group may be optionally substituted.
The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.
The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 or 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the aryl group may be optionally substituted.
The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to three heteroatoms, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Additionally, the heteroaryl group may be optionally substituted.
The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be optionally substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R1 is mono-substituted, then one R1 must be other than H. Similarly, where R1 is di-substituted, then two of R1 must be other than H. Similarly, where R1 is unsubstituted, R1 is hydrogen for all available positions.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, 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[fh]quinoxaline and dibenzo[fh]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.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In comparison to bidentate ligands, tetradentate complexes are demonstrated to have superior emissive properties. Although not wishing to be bound by any particular theory, this effect is believed to be due to a distortion of the square planar geometry in the excited state that leads to non-radiative decay. It is hypothesized that the tetradentate configuration inhibits this distortion, resulting in improved emissive properties when compared to an analogous bis-bidentate structure. In some bis-bidentate and symmetric tetradentate imidazole phenanthridine platinum complexes, the emission energy is not blue enough for display and lighting applications. Therefore, the present invention is based in part on the discovery that substituting nitrogen in the imidazole phenanthridine ring system to form an azaphenanthridine imidazole ligand provides a strong blue-shifting effect not observed in the imidazole phenanthridine ring system.
Substitution of nitrogen in a specific position in the polycyclic azaphenanthridine imidazole ligand system can lead to a profound blue shifting effect. However, the uncoordinated nitrogen presents a stability issue as it may be susceptible to protonation in the excited state. The three ring structure of azaphenanthridine imidazole has a site that, when substituted with a bulky group, such as an aryl ring, shields the uncoordinated nitrogen from the protons of neighboring molecules. Therefore, this type of substitution in this position is useful for improving stability by preventing the uncoordinated nitrogen from being protonated. In addition, substituting a conjugating aryl ring at this position requires that the ring is fully twisted out of plane; therefore, aryl substitution at this site does not lower the triplet energy of the complex. Therefore, the present invention is also based in part on the discovery that the azaphenanthridine imidazole ligand may be a useful scaffold where a substituent on the ligand can be used to sterically block the potentially reactive site of the ligand without lowering the triplet energy.
Compounds of the Invention:
The compounds of the present invention may be synthesized using techniques well-known in the art of organic synthesis. The starting materials and intermediates required for the synthesis may be obtained from commercial sources or synthesized according to methods known to those skilled in the art.
In one aspect, the compound of the invention is a compound having the formula:




wherein A and B are independently selected from the group consisting of a 5-membered or 6-membered carbocyclic or heterocyclic ring;
wherein one of A and B is an anionic coordinating atom, and the other of A and B is a neutral coordinating atoms;
wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution, or no substitution;
wherein R1, R2, R3, R′, and R′′ 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 any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.
In some embodiments, a substituent on the azaphenanthridine imidazole ligand can be used to sterically block the potentially reactive site of the ligand without lowering the triplet energy. In one embodiment, R4 may be a bulky group, such as an aryl substituent, that inhibits close contact of protons from the uncoordinated nitrogen:




In one embodiment, the compound has the formula:




wherein R 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.
In one embodiment, R is selected from the group consisting of alkyl, cycloalkyl, silyl, aryl, heteroaryl, and combinations thereof. In another embodiment, R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof.
In one embodiment, the compound is selected from the group consisting of:




wherein R6 represents mono, di, tri, or tetra-substitution, or no substitution;
wherein R4, R5, and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein any adjacent R4, R5, and R6 are optionally joined to form a ring.
A-B is not particularly limited, as long as A and B are independently selected from the group consisting of a 5-membered or 6-membered carbocyclic or heterocyclic ring, and one of A and B is an anionic coordinating atom, and the other of A and B is a neutral coordinating atoms. In some embodiments, A-B is the same ligand as the azaphenanthridine imidazole ligand. In other embodiments, A-B is a different ligand from the azaphenanthridine imidazole ligand. A-B may be connected to the azaphenanthridine imidazole ring system through X, Y, or both to form a tetradentate ligand. Additionally, A-B may be optionally substituted, and any adjacent substituents may be optionally fused or joined to form a ring. X and Y are not particularly limited, as long as they are capable of linking A-B to the azaphenanthridine imidazole ring system. In one embodiment, only one of X and Y is present. In one embodiment, X is present. In another embodiment, Y is present. In another embodiment, both X and Y are present.
In one embodiment, A-B is selected from the group consisting of:







wherein each X1 to X13 are independently selected from the group consisting of carbon and nitrogen;
wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, SiR′R′′, and GeR′R′′;
wherein R′ and R′′ are optionally fused or joined to form a ring;
wherein each Ra, Rb, Rc, and Rd may represent from mono substitution to the possible maximum number of substitution, or no substitution;
wherein RL represents mono substitution, or no substitution;
wherein Ra, Rb, Rc, Rd and RL 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 when Ra, Rb, Rc, and Rd represent at least di substitution, each of the two adjacent Ra, two adjacent Rb, two adjacent Rc, and two adjacent Rd are optionally fused or joined to form a ring;
wherein RL is optionally a linker to function as X or Y; and
wherein when X1 to X13 are used to link to X or Y, that X1 to X13 is carbon.
In one embodiment, the compound has the formula:




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














































In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Devices:
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 may include a host and a phosphorescent dopant. The emissive 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 electronic component module, 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 be a charge transporting layer and the compound can be a charge transporting material in the organic layer in some embodiments. The organic layer can be a blocking layer and the compound can be a blocking material in the organic layer in some 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, and 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 comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be a specific compound selected from the group consisting of:













and combinations thereof.

Formulations:

In yet another aspect of the present disclosure, a formulation that comprises 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, and an electron transport layer material, disclosed herein.
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 are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to the following general structures:




Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of 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 the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:




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

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




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

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




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

In one aspect, the metal complexes are:




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

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
Examples of organic compounds used as host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of 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 the group consisting of 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, the host compound contains at least one of the following groups in the molecule:







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

HBL:

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




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

ETL:

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




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

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




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

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









TABLE A





MATER-

PUBLICA-


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EXAMPLES OF MATERIAL
TIONS















Hole injection materials









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Phosphonic  acid and  silane SAMs




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n-type  semi- conducting organic  complexes




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Metal  organo- metallic complexes




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Red hosts









Aryl- carbazoles




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Zinc  complexes




WO2010056066


 


Chrysene  based compounds




WO2011086863


 







Green hosts









Aryl- carbazoles




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Aryl- tri- phenylene compounds




US20060280965


 







US20060280965


 







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Poly-fused  heteroaryl compounds




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Donor  acceptor  type molecules




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Aza- carbazole/ DBT/DBF




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Polymers  (e.g., PVK)




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Spiro- fluorene  compounds




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Metal phenoxy- benzo- oxazole compounds




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Spiro- fluorene- carbazole compounds




JP2007254297


 







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Indolo- carbazoles




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Tetra- phenylene  complexes




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Metal  phenoxy- pyridine compounds




WO2005030900


 


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




US20040137268, US20040137267


 







Blue hosts









Aryl- carbazoles




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Dibenzo- thiophene/ Di- benzofuran- carbazole compounds




WO2006114966, US20090167162


 







US20090167162


 







WO2009086028


 







US20090030202, US20090017330


 







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Silicon  aryl  com- pounds




US20050238919


 







WO2009003898


 


Silicon/ Ger- manium  aryl compounds




EP2034538A


 


Aryl  benzoyl  ester




WO2006100298


 


Carbazole  linked  by non- conjugated  groups




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Aza- carbazoles




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Red dopants









Heavy  metal  porphyrins (e.g.,  PtOEP)




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


 







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Ruthenium (II)  complexes




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EXPERIMENTAL
In Formula I, azaphenanthridine imidazole is linked through the imidazole or pyridyl ring through X or Y or both to form a tetradentate ligand coordinated to M. Preferably, M=Pt, Pd. The ligand precursors and the inventive metal complexes of the general Formula I may be prepared by processes known to those skilled in the art. Suitable processes are mentioned, for example, in WO2012116231, which is incorporated by reference herein in its entirety, and the literature cited therein for general tetradentate Pt complexation. The inventive metal complexes can be purified by processes known to those skilled in the art. Typically, the workup and purification are affected by extraction, column chromatography, recrystallization, and/or sublimation by processes known to those skilled in the art.
An exemplary process for preparing the inventive metal complexes containing a ligand according to Formula I is detailed below by using a synthetic path shown below:










The benzyl or 4-methoxybenzyl protected hydroxynicotinonitrile can be prepared according to the method of Baldwin et al. (U.S. Pat. No. 4,374,140, which is incorporated by reference herein in its entirety). Reaction of this with the boronic ester and a palladium catalyst would give the azaphenanthridine. The preparation of the tribromoaldehyde is given in Tsai et al. (U.S. Patent Application No. 20100148663, which is incorporated by reference herein in its entirety). Reaction of the aldehyde with phenanthridine in isopropanol would give the azaimidazophenanthridine. Reaction of this with isopropenylboronic acid pinacol ester would give the isopropenyl substituted intermediate. Hydrogenation of this would simultaneously reduce the olefins and remove the benzyl or 4-methoxybenzyl group. The phenol can be treated with triflic anhydride and triethylamine to give the triflate. The triflate can be converted to the iodide using the methodology of Thompson et al. (Synthesis (4) pp 547-550 (2005), which is incorporated by reference herein in its entirety). The iodide can be coupled with the phenol using the method of Altman et al. (Organic Letters 9 (4) pp 643-646 (2007), which is incorporated by reference herein in its entirety). Metallation with a Platinum source such as K2PtCl4 in acetic acid would afford the final complex.
Several comparative examples are provided.
Comparative example 1 is a bis-bidentate imidazole phenanthridine platinum complex. It is nonemissive in room temperature solution and only weakly emissive in the solid state. The 77 K emission spectrum for Comparative Example 1 is provided in FIG. 3. The highest energy peak emission is 472 nm.




The emissive properties of Comparative Example 1 are compared directly to Comparative Example 2. Comparative Example 2 is a symmetric tetradentate imidazole phenanthridine platinum complex where the imidazole phenanthridines are bridged by oxygen to provide one tetradentate ligand.




In comparison to Comparative Example 1, Comparative Example 2 is brightly emissive in room temperature solution and has a very high PLQY doped in PMMA matrix of 84%.
The emission spectra in solid state PMMA matrix, and 77 K and room temperature 2-methyl tetrahydrofuran (THF) solvent are shown in FIG. 4. The highest energy peak emission in solid state PMMA matrix is 480 nm.
One drawback for both Comparative Examples 1 and 2 is that the emission energy is not blue enough for display and lighting applications. The results described herein demonstrate that substituting nitrogen in the ring system provides a strong blue-shifting effect not observed in compounds such as Comparative Examples 1 and 2, where there is no additional nitrogen in the ring system.
Density functional theory (DFT) calculations are shown in Table 1. DFT calculations were performed using the B3LYP/cep-31g/THF functional, basis set and solvent polarization, respectively.
The blue-shifting effect of the uncoordinated nitrogen is clearly shown in density functional theory (DFT) calculations by comparing the triplet energies of invention Compounds 1-3 to Comparative Example 2. As shown in Table 1, Compounds 1-3 have calculated triplet energies in the range of 480 nm, while the triplet energy of Comparative Example 2 is calculated to be 497 nm.
In order to calibrate calculated values to experimental results, the experimentally determined triplet energy of Comparative Example 2 is 480 nm, as shown in FIG. 4. Furthermore, DFT and experimental results for a blue-shifted asymmetric derivative, Comparative Example 3, are shown in Table 1 and FIG. 5. Comparative Example 3 is calculated by DFT to have a triplet of 479 nm. In room temperature and 77 K 2-methyl tetrahydrofuran solvent, the triplet is experimentally determined to be 456 and 451 nm, respectively. In one embodiment, the invention compounds described here are in a desirable blue emission range of 450-470 nm. Another advantage for the compounds of the invention are that they can be designed as symmetric structures, unlike the blue emissive Comparative Example 3. This can be beneficial for synthetic and stability reasons.
It can be seen in space filling models of Compound 2, calculated by density functional theory (DFT), that an aryl substituent sterically shields the uncoordinated nitrogen from close contact of a neighboring intra or intermolecular proton atom. This site blocking substituent may be a desirable feature for improving the stability. Furthermore, as the aryl substitution at this site necessarily twists out of the plane of the ligand, there is a minimal effect on the triplet energy of the complex. It is shown in Table 1 that the calculated triplet for an aryl substituted compound, Compound 2, is nearly identical to the methyl substituted analogue, Compound 1.
The calculated and experimental data for Comparative Example 5, an iridium analogue with an azaphenanthridine imidazole ligand, is also shown for comparison to the tetradentate platinum complex. DFT calculations for Comparative Example 5, the meridional (mer) isomer of tris iridium imidazole aza-phenanthridine complexes, predict a triplet energy of 448 nm. Furthermore, the experimental 77 K solution emission spectrum is shown in FIG. 6. The highest energy peak emission for Comparative Example 5 is 431 nm. Comparative Example 5 is nonemissive in room temperature solution. Therefore, while Comparative Example 5 has deep blue emission, it is actually too high in energy to be supported by conventional host materials that typically contain carbazole, dibenzofuran and dibenzothiophene moieties, due to triplet quenching. Based on the predicted triplet energy, the tetradentate platinum system is not expected to suffer from this limitation, and is expected to emit with high photoluminescent efficiency compared to a bidentate analogue.







TABLE 1







Density functional theory (DFT) calculations
















HOMO
LUMO
Gap
Dipole
S1THF
T1THF



Structure
(eV)
(ev)
(ev)
(Debye)
(nm)
(nm)





Compound 1




−5.74
−1.94
−3.80
 9.19
402
481


 


Compound 2




−5.75
−1.95
−3.79
10.23
403
482


 


Compound 3




−5.75
−1.95
−3.80
11.42
403
481


 


Comparative Example 2




−5.28
−1.60
−3.67
 6.70
420
497


 


Comparative Example 3




−5.28
−1.65
−3.62
10.19
418
479


 


Comparative Example 4




−5.56
−1.52
−4.04
10.35
411
447


 


Comparative Example 5




−5.57
−1.50
−4.08
 6.03
390
448









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.
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention. The appended claims are intended to be construed to include all such embodiments and equivalent variations.

## Claims

1. A compound of Formula II:



wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution;
wherein R1, R2, R3, R′, and R′′ 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, and phosphino; and
wherein any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.

2. The compound of claim 1, wherein M is Pt.

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



wherein R 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, and phosphino.

4. The compound of claim 3, wherein R is selected from the group consisting of alkyl, cycloalkyl, silyl, aryl, and heteroaryl.

5. The compound of claim 3, wherein R is selected from the group consisting of methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, and 2,6-diisopropylphenyl.

6. The compound of claim 1, wherein only one of X and Y is present.

7. The compound of claim 3, wherein the compound is selected from the group consisting of:



wherein R6 represents mono, di, tri, or tetra-substitution, or no substitution;
wherein R4, R5, and R6 are each independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and phosphino; and
wherein any adjacent R4, R5, and R6 are optionally joined to form a ring.

8. A compound selected from the group consisting of:

9. A device comprising an organic light emitting device, the organic light emitting device comprising:
an anode;
a cathode; and
an organic layer, disposed between the anode and the cathode, the organic comprising a compound of Formula II:




wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution, or no substitution;
wherein R2 represent mono, di, tri, or tetra-substitution;
wherein R1, R2, R3, R′, and R′′ 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, and phosphino; and
wherein any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.

10. The device of claim 9 selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.

11. The device of claim 9, wherein the organic layer further comprises a host; wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan;
wherein any substituent in the host is an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1—Ar2, CnH2n—Ar1, or no substitution;
wherein n is from 1 to 10; and
wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

12. The device of claim 9, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.

13. The device of claim 9, wherein the organic layer further comprises a host and the host is selected from the group consisting of:












and combinations thereof.

14. A formulation comprising the compound of Formula II:



wherein X and Y are independently selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R′′, alkyl, aryl, SiR′R′′, and GeR′R′′;
wherein at least one of X and Y is present;
wherein M is Pt or Pd;
wherein R1 and R3 each independently represent mono, or di-substitution;
wherein R2 represent mono, di, tri, or tetra-substitution;
wherein R1, R2, R3, R′, and R′′ 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, and phosphino; and
wherein any adjacent R1, R2, R3, R′, and R′′ are optionally joined to form a ring.

15. The compound of claim 1 having a calculated Debye dipole of from 9.19 to 11.42 as determined by Density Functional Theory.

16. The compound of claim 1 having a triplet blue emission in a range of 450 nm to 482 nm.

17. The device of claim 9, wherein the compound of Formula II has a triplet blue emission in a range of 450 nm to 482 nm, and a calculated Debye dipole of from 9.19 to 11.42 as determined by Density Functional Theory.

18. The device of claim 17, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.