# Patent

## Title
Organic electroluminescent materials and devices

## Abstract

Novel oligocarbazole compounds containing a triphenylene and an oligocarbazole are provided. The compounds are useful in devices including organic light emitting devices (OLEDs).

## Background
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, The University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.
FIELD OF THE INVENTION
The present invention relates to novel organic compounds containing a triphenylene and an oligocarbazole. The compounds are useful in devices including organic light emitting devices (OLEDs).
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, 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.
BRIEF SUMMARY OF THE INVENTION
A new class of compounds containing a triphenylene and an oligocarbazole moiety are provided.
The present invention provides compounds having formula I:

A-L-C  (I).

In the compound of formula I, A has the formula:





C has the formula:





L has the formula:





R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.
In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deuterium, phenyl, and combinations thereof.
In some embodiments, R1, R2, R3, R4, R5, and R6 are hydrogen.
In some embodiments, L is selected from the group consisting of phenyl and pyridine.
In some embodiments, L is selected from the group consisting of:




In some embodiments, A is selected from the group consisting of:










In some embodiments, A is selected from the group consisting of:










L is selected from the group consisting of:





and

C is selected from the group consisting of:





In some embodiments, the compound of formula I is selected from the group consisting of Compound 1 to Compound 200 listed in TABLE 1.
In some embodiments, the compound of formula I has the formula:




In some embodiments, a first device is provided. The first device comprises a first organic light emitting device, further comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the formula:

A-L-C  (I).

In the compound of formula I, A has the formula:





C has the formula:





L has the formula:





R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, the organic layer of the device is an emissive layer and the compound of the formula I is a host.
In some embodiments, the organic layer of the device further comprises a phosphorescent emissive dopant.
In some embodiments, the phosphorescent emissive dopant of the device is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:










wherein Ra, Rb, Rc, and Rd may represent mono, di, tri, or tetra substitution, or no substitution;
wherein Ra, Rb, Rc, and Rd are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein two adjacent substituents of Ra, Rb, Rc, and Rd are optionally joined to form a fused ring or form a multidentate ligand.
In some embodiments, the organic layer of the device is a blocking layer and the compound is a blocking material in the organic layer.
In some embodiments, the device is a consumer product.
In some embodiments, the device is an organic light-emitting device.
In some embodiments, the device comprises a lighting panel.
In some embodiments, the device comprises a compound of formula I which is:




In some embodiments, a formulation comprising a compound having the formula:

A-L-C  (I)

is provided.




BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated herein and form a part of the specification, illustrate embodiments of the present invention and, together with the description, further serve to explain the principles of the invention and to enable a person skilled in the pertinent art to make and use the invention.
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-A.



DETAILED DESCRIPTION
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
FIG. 2 shows an inverted OLED 200, The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200, FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.
The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In some embodiments, 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 OVJP. 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 processability 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, 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 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, aralkyl, 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.
As used herein, “substituted” indicates that a substituent other than His 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.
A wide variety of carboxylic and heterocyclic functional groups, including triphenylene and carbazole, have been used to synthesize compound for organic electroluminescent materials. Depending on the unique ways building blocks are connected, these compounds have different thermal stability, energy levels, molecular packing, and charge-transport properties, all of which heavily influence device performance. This invention discloses a new class of compounds where triphenylene is connected to an oligocarbazole through an appropriate aromatic linking unit. Unexpectedly, phosphorescent OLED devices using the compounds of the invention as host materials demonstrate superior stability compared to the compounds reported in the literature. The enhanced device performance may be due to boosted intrinsic materials stability and improved charge carrier balance.
In some embodiments, a compound having the formula:

A-L-C  (I)

is provided. In the compound of formula I, A has the formula:





C has the formula:





and L has the formula:





R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, and combinations thereof; and Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, a compound having the formula I-A:




is provided. In the compound of formula I-A, R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deterium, aryl, heteroaryl, and combinations thereof.
In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deuterium, phenyl, and combinations thereof.
In some embodiments, R1, R2, R3, R4, R5, R6, R7, R8 and R9 are hydrogen.
In some embodiments, L is selected from the group consisting of phenyl and pyridine.
In some embodiments, L is selected from the group consisting of:




In some embodiments, A is selected from the group consisting of:










In some embodiments, A is selected from the group consisting of:










L is selected from the group consisting of:





and

C is selected from the group consisting of:





In some embodiments, A is selected from the group consisting of:










In some embodiments, A is A1.

In some embodiments, L is selected from the group consisting of:




In some embodiments, L is L1.

In some embodiments, C is selected from the group consisting of:




In some embodiments, C is C1.

In some embodiments, A is A1, L is L1, and C is C1.
In some embodiments, the compound is selected from the group consisting of Compound 1 to Compound 200 listed in TABLE 1.












TABLE 1







Comp #
A
L
C









Comp 1
A1
L1
C1



Comp 2
A2
L1
C1



Comp 3
A3
L1
C1



Comp 4
A4
L1
C1



Comp 5
A5
L1
C1



Comp 6
A6
L1
C1



Comp 7
A7
L1
C1



Comp 8
A8
L1
C1



Comp 9
A9
L1
C1



Comp 10
A10
L1
C1



Comp 11
A1
L2
C1



Comp 12
A2
L2
C1



Comp 13
A3
L2
C1



Comp 14
A4
L2
C1



Comp 15
A5
L2
C1



Comp 16
A6
L2
C1



Comp 17
A7
L2
C1



Comp 18
A8
L2
C1



Comp 19
A9
L2
C1



Comp 20
A10
L2
C1



Comp 21
A1
L3
C1



Comp 22
A2
L3
C1



Comp 23
A3
L3
C1



Comp 24
A4
L3
C1



Comp 25
A5
L3
C1



Comp 26
A6
L3
C1



Comp 27
A7
L3
C1



Comp 28
A8
L3
C1



Comp 29
A9
L3
C1



Comp 30
A10
L3
C1



Comp 31
A1
L4
C1



Comp 32
A2
L4
C1



Comp 33
A3
L4
C1



Comp 34
A4
L4
C1



Comp 35
A5
L4
C1



Comp 36
A6
L4
C1



Comp 37
A7
L4
C1



Comp 38
A8
L4
C1



Comp 39
A9
L4
C1



Comp 40
A10
L4
C1



Comp 41
A1
L5
C1



Comp 42
A2
L5
C1



Comp 43
A3
L5
C1



Comp 44
A4
L5
C1



Comp 45
A5
L5
C1



Comp 46
A6
L5
C1



Comp 47
A7
L5
C1



Comp 48
A8
L5
C1



Comp 49
A9
L5
C1



Comp 50
A10
L5
C1



Comp 51
A1
L1
C2



Comp 52
A2
L1
C2



Comp 53
A3
L1
C2



Comp 54
A4
L1
C2



Comp 55
A5
L1
C2



Comp 56
A6
L1
C2



Comp 57
A7
L1
C2



Comp 58
A8
L1
C2



Comp 59
A9
L1
C2



Comp 60
A10
L1
C2



Comp 61
A1
L2
C2



Comp 62
A2
L2
C2



Comp 63
A3
L2
C2



Comp 64
A4
L2
C2



Comp 65
A5
L2
C2



Comp 66
A6
L2
C2



Comp 67
A7
L2
C2



Comp 68
A8
L2
C2



Comp 69
A9
L2
C2



Comp 70
A10
L2
C2



Comp 71
A1
L3
C2



Comp 72
A2
L3
C2



Comp 73
A3
L3
C2



Comp 74
A4
L3
C2



Comp 75
A5
L3
C2



Comp 76
A6
L3
C2



Comp 77
A7
L3
C2



Comp 78
A8
L3
C2



Comp 79
A9
L3
C2



Comp 80
A10
L3
C2



Comp 81
A1
L4
C2



Comp 82
A2
L4
C2



Comp 83
A3
L4
C2



Comp 84
A4
L4
C2



Comp 85
A5
L4
C2



Comp 86
A6
L4
C2



Comp 87
A7
L4
C2



Comp 88
A8
L4
C2



Comp 89
A9
L4
C2



Comp 90
A10
L4
C2



Comp 91
A1
L5
C2



Comp 92
A2
L5
C2



Comp 93
A3
L5
C2



Comp 94
A4
L5
C2



Comp 95
A5
L5
C2



Comp 96
A6
L5
C2



Comp 97
A7
L5
C2



Comp 98
A8
L5
C2



Comp 99
A9
L5
C2



Comp 100
A10
L5
C2



Comp 101
A1
L1
C3



Comp 102
A2
L1
C3



Comp 103
A3
Li
C3



Comp 104
A4
L1
C3



Comp 105
A5
L1
C3



Comp 106
A6
L1
C3



Comp 107
A7
L1
C3



Comp 108
A8
L1
C3



Comp 109
A9
L1
C3



Comp 110
A10
L1
C3



Comp 111
A1
L2
C3



Comp 112
A2
L2
C3



Comp 113
A3
L2
C3



Comp 114
A4
L2
C3



Comp 115
A5
L2
C3



Comp 116
A6
L2
C3



Comp 117
A7
L2
C3



Comp 118
A8
L2
C3



Comp 119
A9
L2
C3



Comp 120
A10
L2
C3



Comp 121
A1
L3
C3



Comp 122
A2
L3
C3



Comp 123
A3
L3
C3



Comp 124
A4
L3
C3



Comp 125
A5
L3
C3



Comp 126
A6
L3
C3



Comp 127
A7
L3
C3



Comp 128
A8
L3
C3



Comp 129
A9
L3
C3



Comp 130
A10
L3
C3



Comp 131
A1
L4
C3



Comp 132
A2
L4
C3



Comp 133
A3
L4
C3



Comp 134
A4
L4
C3



Comp 135
A5
L4
C3



Comp 136
A6
L4
C3



Comp 137
A7
L4
C3



Comp 138
A8
L4
C3



Comp 139
A9
L4
C3



Comp 140
A10
L4
C3



Comp 141
A1
L5
C3



Comp 142
A2
L5
C3



Comp 143
A3
L5
C3



Comp 144
A4
L5
C3



Comp 145
A5
L5
C3



Comp 146
A6
L5
C3



Comp 147
A7
L5
C3



Comp 148
A8
L5
C3



Comp 149
A9
L5
C3



Comp 150
A10
L5
C3



Comp 151
A1
L1
C4



Comp 152
A2
L1
C4



Comp 153
A3
L1
C4



Comp 154
A4
L1
C4



Comp 155
A5
L1
C4



Comp 156
A6
L1
C4



Comp 157
A7
L1
C4



Comp 158
A8
L1
C4



Comp 159
A9
L1
C4



Comp 160
A10
L1
C4



Comp 161
A1
L2
C4



Comp 162
A2
L2
C4



Comp 163
A3
L2
C4



Comp 164
A4
L2
C4



Comp 165
A5
L2
C4



Comp 166
A6
L2
C4



Comp 167
A7
L2
C4



Comp 168
A8
L2
C4



Comp 169
A9
L2
C4



Comp 170
A10
L2
C4



Comp 171
A1
L3
C4



Comp 172
A2
L3
C4



Comp 173
A3
L3
C4



Comp 174
A4
L3
C4



Comp 175
A5
L3
C4



Comp 176
A6
L3
C4



Comp 177
A7
L3
C4



Comp 178
A8
L3
C4



Comp 179
A9
L3
C4



Comp 180
A1
L3
C4



Comp 181
A1
L4
C4



Comp 182
A2
L4
C4



Comp 183
A3
L4
C4



Comp 184
A4
L4
C4



Comp 185
A5
L4
C4



Comp 186
A6
L4
C4



Comp 187
A7
L4
C4



Comp 188
A5
L4
C4



Comp 189
A9
L4
C4



Comp 190
A10
L4
C4



Comp 191
A1
L5
C4



Comp 192
A2
L5
C4



Comp 193
A3
L5
C4



Comp 194
A4
L5
C4



Comp 195
A5
L5
C4



Comp 196
A6
L5
C4



Comp 197
A7
L5
C4



Comp 198
A8
L5
C4



Comp 199
A9
L5
C4



Comp 200
A10
L5
C4










In some embodiments, the compound of formula I is:




In some embodiments, a first device is provided. The first device comprises a first organic light emitting device, further comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound of the formula:

A-L-C  (I).

In the compound of formula I, A has the formula:





C has the formula:





L has the formula:





R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z′, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, the first device comprises a first organic light emitting device, further comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound of the formula:




In the compound of formula I-A, R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution; R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution; m is an integer from 0 to 10; R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrite, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

In some embodiments, the organic layer of the device is an emissive layer and the compound of the formula I is a host.
In some embodiments, the organic layer of the device further comprises a phosphorescent emissive dopant.
In some embodiments, the phosphorescent emissive dopant of the device is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:










wherein Ra, Rb, Rc, and Rd may represent mono, di, tai, or tetra substitution, or no substitution; wherein Ra, Rb, Rc, and Rd are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein two adjacent substituents of Ra, Rb, Rc, and Rd are optionally joined to form a fused ring or form a multidentate ligand.

In some embodiments, the organic layer of the first device is a blocking layer and the compound is a blocking material in the organic layer.
In some embodiments, the first device is a consumer product. In some embodiments, the first device is an organic light-emitting device. In some embodiments, the first device comprises a lighting panel.
In some embodiments, the first device comprises the compound:




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, faran, 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 some embodiments, Ar1 to Ar9 is independently selected from the group consisting of:




k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:




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




Met is a metal; (Y103-Y104) is a bidentate ligand, 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 some embodiments, the metal complexes are:




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







R101 to R107 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
k is an integer from 1 to 20; k′′′ is an integer from 0 to 20.
X101 to X108 is selected from C (including CH) or N.
Z101 and Z102 are 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 some embodiments, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In some embodiments, compound used in HBL contains at least one of the following groups in the molecule:




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




R101 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
Ar1 to Ar3 has the similar definition as Ar's mentioned above.
k is an integer from 1 to 20.
X101 to X108 is selected from C (including CH) or N.
In some embodiments, the metal complexes used in ETL contains, but not limit to the following general formula:




(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.
In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in TABLE 2 below. TABLE 2 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.









TABLE 2





MATERIAL
EXAMPLES OF MATERIAL
PUBLICATIONS















Hole injection materials









Phthalocyanine and porphryin compounds




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


 


Starburst triarylamines




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


 


CFx Fluorohydrocarbon polymer




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


 


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




Synth. Met. 87,  171 (1997) WO2007002683


 


Phosphonic acid  and sliane SAMs




US20030162053


 


Triarylamine or polythiophene polymers with conductivity  dopants



   and
EP1725079A1


 










 










 


Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides




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


 


n-type semiconducting organic complexes




US20020158242


 


Metal organometallic complexes




US20060240279


 


Cross-linkable  compounds




US20080220265


 


Polythiophene based polymers and  copolymers




WO 2011075644 EP2350216


 







Hole transporting materials









Triarylamines (e.g., TPD, □-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/ DRT/DBF




JP2008074939


 







US20100187984


 


Polymers (e.g., PVK)




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


 


Spirofluorene  compounds




WO2004093207


 


Metal phenoxybenzooxazole compounds




WO2005089025


 







WO2006132173


 







JP200511610


 


Spirofluorene- carbazole compounds




JP2007254297


 







JP2007254297


 


Indolocabazoles




WO2007063796


 







WO2007063754


 


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




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


 







WO2004107822


 


Tetraphenylene  complexes




US20050112407


 


Metal phenoxypyridine compounds




WO2005030900


 


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




US20040137268, US20040137267


 







Blue hosts









Arylcarbazoles




Appl. Phys. Lett  82, 2422 (2003)


 







US20070190359


 


Dibenzothiophene/ Dibenzofuran- carbazole compounds




WO2006114966, US20090167162


 







US20090167162


 







WO2009086028


 







US20090030202, US20090017330


 







US20100084966


 


Silicon aryl  compounds




US20050238919


 







WO2009003898


 


Silicon/Germanium  aryl compounds




EP2034538A


 


Aryl benzoyl ester




WO2006100298


 


Carbazole linked by non-conjugated groups




US20040115476


 


Aza-carbazoles




US20060121308


 


High triplet metal organometallic  complex




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


 







Phosphorescent dopants


Red dopants









Heavy metal  porphyrins (e.g., PtOEP)




Nature 395, 151  (1998)


 


Iridium(III)  organometallic complexes




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


 







US2006835469


 







US2006835469


 







US20060202194


 







US20060202194


 







US20070087321


 







US20080261076 US20100090591


 







US20070087321


 







Adv. Mater. 19,  739 (2007)


 







WO2009100991


 







WO2008101842


 







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


 


Platinum(II) organometallic  complexes




WO2003040257


 







US20070103060


 


Osminum(III)  complexes




Chem. Mater. 17,  3532 (2005)


 


Ruthenium(II)  complexes




Adv. Mater. 17,  1059 (2005)


 


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




US20050244673


 







Green dopants









Iridium(III)  organometallic complexes



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


 







US20020034656


 







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


 







US20090108737


 







WO2010028151


 







EP1841834B


 







US20060127696


 







US20090039776


 







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


 







US20100244004


 







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


 







Chem. Mater. 16,  2480 (2004)


 







US20070190359


 







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, 153505 (2005)


 







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


 







Chem. Lett. 34,  592 (2005)


 







WO2002015645


 







US20060263635


 







US20060182992 US20070103060


 


Cu complexes




WO2009000673


 







US20070111026


 


Gold complexes




Chem. Commun.  2906 (2005)


 


Rhenium(III)  complexes




Inorg. Chem. 42,  1248 (2003)


 


Osmium(II)  complexes




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


 


Deuterated  organometallic complexes




US20030138657


 


Organometallic  complexes with  two or more metal centers




US20030152802


 







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


 







Blue dopants









Iridium(III)  organometallic complexes




WO2002002714


 







WO2006009024


 







US20060251923 US20110057559 US20110204333


 







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


 







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


 







WO2011051404


 







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


 







US20070190359, US20080297033 US20100148663


 







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


 







US20020134984


 







Angew. Chem.  Int. Ed. 47, 4542 (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, b3745 (2004)


 


Gold complexes




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


 


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EXPERIMENTAL
Chemical abbreviations used throughout this document are as follows: SPhos is dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine and Pd2(dba)3 is tri(dibenzylideneacetone)dipalladium(0).
Synthesis of Comp 1




A solution of 2-(4-bromophenyl)triphenylene (1.78 g, 4.64 mmol), 9H-3,9′-bicarbazole (1.70 g, 5.11 mmol), Pd2(dba)3 (0.17 g, 0.19 mmol), SPhos (0.15 g, 0.37 mmol), and sodium tert-butoxide (1.34 g, 13.93 mmol) in xylene (150 ml) was refluxed overnight. The hot reaction mixture was filtered through a plug of silica gel and the solvent was evaporated. The crude product was purified by precipitation in heptane to yield Comp 1 (2.60 g, 88%) as a white solid.
Device Examples
All devices were fabricated by high vacuum ( ̃10−7 Torr) thermal evaporation. The anode electrode was 120 nm of indium tin oxide (ITO). The cathode electrode consisted of 1 nm of LiF followed by 100 nm 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.
All device examples had organic stacks consisting of, sequentially, from the ITO surface, 10 nm of Compound A as the hole injection layer (HIL), 30 nm of 4,4′-bis[N-(1-naphthyl)-N-phenylaminolbiphenyl (NPD) as the hole-transport layer (HTL), and 30 nm of inventive hosts (Comp 1) or comparative hosts (CC-1, CC-2, and CC-3) doped with 15 wt % of Compound A as the emissive layer (EML). On top of the EML, 5 nm of Compound BL was deposited as the hole blocking layer (HBL), followed by 45 nm of tris(8-hydroxyquinolinato)aluminum (Alq3) as the electron-transport layer (ETL).
The chemical structures of the compounds used in the devices are as follows:







Thermal Properties of Compounds
The glass transition temperatures (Tg) of selected compounds were measured using differential scanning calorimetery (DSC) during a heating scan at 10° C./min and the results are recorded in TABLE 3.







TABLE 3







Glass Transition Temperatures of Compounds.










Compound
Tg, ° C.







CC-1
154



CC-2
155



CC-3
158



Comp 1
160










Unexpectedly, Comp 1 has a higher Tg than comparative examples CC-1, CC-2, and CC-3, suggesting that the inventive chemical structure is favorable for a high Tg. It is worth noting that Comp 1 has a molecular weight less than CC-3. On the other hand, it is widely accepted that, used at the same temperature, organic materials with high Tg are less prone to undergo phase transition, e.g. crystallization. Therefore, the inventive compound is more suitable than the comparative counterparts to build OLEDs operable in a higher-temperature environment.
Device Performance
TABLE 4 provides a summary of the relative device data, where emission color, external quantum efficiency (EQE) was recorded at 1000 nits, while the lifetime (LT80%) defined as the time required for the device to decay to 80% of its initial luminance was measured at a constant current density of 40 mA/cm2. All device data are normalized on those of comparative Device C-1.











TABLE 4









LT80% at 40


Devices
Host
Color
EQE at 1000 nits
mA/cm2



















Device C-1
CC-1
Green
100
100


Device C-2
CC-2
Green
113
149


Device C-3
CC-3
Green
99
143


Device 1
Comp 1
Green
112
240









All devices emit green color. As shown in TABLE 4, Device 1 which uses inventive Comp 1 as host material shows equivalent or better efficiency, and significantly improved lifetime, as compared to devices C-1, C-2, and C-3 using comparative compounds as hosts. This enhanced device performance might be attributable to improved charge balance and materials stability (e.g., higher glass transition temperature), owing to the unique chemical structures of the invented compounds, which is unexpected.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

## Claims

1. A compound having the formula:


A-L-C  (I);

wherein A has the formula:




wherein C has the formula:




wherein L has the formula:




wherein R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution;
wherein R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution;
wherein m is 0;
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

2. The compound of claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deuterium, aryl, heteroaryl, and combinations thereof.

3. The compound of claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently selected from the group consisting of hydrogen, deuterium, phenyl, and combinations thereof.

4. The compound of claim 1, wherein R1, R2, R3, R4, R5, and R6 are hydrogen.

5. The compound of claim 1, wherein L is selected from the group consisting of phenyl and pyridine.

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

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

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









wherein L is selected from the group consisting of:





and
wherein C is selected from the group consisting of:

9. The compound of claim 8, wherein the compound is selected from the group consisting of Compound 1 to Compound 5, Compound 10 to Compound 15, Compound 20 to Compound 25, Compound 30 to Compound 35, Compound 40 to Compound 45, Compound 50 to Compound 55, Compound 60 to Compound 65, Compound 70 to Compound 75, Compound 80 to Compound 85, Compound 90 to Compound 95, Compound 100 to Compound 105, Compound 110 to Compound 115, Compound 120 to Compound 125, Compound 130 to Compound 135, Compound 140 to Compound 145, Compound 150 to Compound 155, Compound 160 to Compound 165, Compound 170 to Compound 175, Compound 180 to Compound 185, Compound 190 to Compound 195, and Compound 200 listed below:
















Comp #
A
L
C









Comp 1
A1
L1
C1



Comp 2
A2
L1
C1



Comp 3
A3
L1
C1



Comp 4
A4
L1
C1



Comp 5
A5
L1
C1



Comp 10
A10
L1
C1



Comp 11
A1
L2
C1



Comp 12
A2
L2
C1



Comp 13
A3
L2
C1



Comp 14
A4
L2
C1



Comp 15
A5
L2
C1



Comp 20
A10
L2
C1



Comp 21
A1
L3
C1



Comp 22
A2
L3
C1



Comp 23
A3
L3
C1



Comp 24
A4
L3
C1



Comp 25
A5
L3
C1



Comp 30
A10
L3
C1



Comp 31
A1
L4
C1



Comp 32
A2
L4
C1



Comp 33
A3
L4
C1



Comp 34
A4
L4
C1



Comp 35
A5
L4
C1



Comp 40
A10
L4
C1



Comp 41
A1
L5
C1



Comp 42
A2
L5
C1



Comp 43
A3
L5
C1



Comp 44
A4
L5
C1



Comp 45
A5
L5
C1



Comp 50
A10
L5
C1



Comp 51
A1
L1
C2



Comp 52
A2
L1
C2



Comp 53
A3
L1
C2



Comp 54
A4
L1
C2



Comp 55
A5
L1
C2



Comp 60
A10
L1
C2



Comp 61
A1
L2
C2



Comp 62
A2
L2
C2



Comp 63
A3
L2
C2



Comp 64
A4
L2
C2



Comp 65
A5
L2
C2



Comp 70
A10
L2
C2



Comp 71
A1
L3
C2



Comp 72
A2
L3
C2



Comp 73
A3
L3
C2



Comp 74
A4
L3
C2



Comp 75
A5
L3
C2



Comp 80
A10
L3
C2



Comp 81
A1
L4
C2



Comp 82
A2
L4
C2



Comp 83
A3
L4
C2



Comp 84
A4
L4
C2



Comp 85
A5
L4
C2



Comp 90
A10
L4
C2



Comp 91
A1
L5
C2



Comp 92
A2
L5
C2



Comp 93
A3
L5
C2



Comp 94
A4
L5
C2



Comp 95
A5
L5
C2



Comp 100
A10
L5
C2



Comp 101
A1
L1
C3



Comp 102
A2
L1
C3



Comp 103
A3
Li
C3



Comp 104
A4
L1
C3



Comp 105
A5
L1
C3



Comp 110
A10
L1
C3



Comp 111
A1
L2
C3



Comp 112
A2
L2
C3



Comp 113
A3
L2
C3



Comp 114
A4
L2
C3



Comp 115
A5
L2
C3



Comp 120
A10
L2
C3



Comp 121
A1
L3
C3



Comp 122
A2
L3
C3



Comp 123
A3
L3
C3



Comp 124
A4
L3
C3



Comp 125
A5
L3
C3



Comp 130
A10
L3
C3



Comp 131
A1
L4
C3



Comp 132
A2
L4
C3



Comp 133
A3
L4
C3



Comp 134
A4
L4
C3



Comp 135
A5
L4
C3



Comp 140
A10
L4
C3



Comp 141
A1
L5
C3



Comp 142
A2
L5
C3



Comp 143
A3
L5
C3



Comp 144
A4
L5
C3



Comp 145
A5
L5
C3



Comp 150
A10
L5
C3



Comp 151
A1
L1
C4



Comp 152
A2
L1
C4



Comp 153
A3
L1
C4



Comp 154
A4
L1
C4



Comp 155
A5
L1
C4



Comp 160
A10
L1
C4



Comp 161
A1
L2
C4



Comp 162
A2
L2
C4



Comp 163
A3
L2
C4



Comp 164
A4
L2
C4



Comp 165
A5
L2
C4



Comp 170
A10
L2
C4



Comp 171
A1
L3
C4



Comp 172
A2
L3
C4



Comp 173
A3
L3
C4



Comp 174
A4
L3
C4



Comp 175
A5
L3
C4



Comp 180
A1
L3
C4



Comp 181
A1
L4
C4



Comp 182
A2
L4
C4



Comp 183
A3
L4
C4



Comp 184
A4
L4
C4



Comp 185
A5
L4
C4



Comp 190
A10
L4
C4



Comp 191
A1
L5
C4



Comp 192
A2
L5
C4



Comp 193
A3
L5
C4



Comp 194
A4
L5
C4



Comp 195
A5
L5
C4



Comp 200
A10
L5
C4.

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

11. A first device comprising 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:


A-L-C  (I);


wherein A has the formula:




wherein C has the formula:




wherein L has the formula:




wherein R1, R2, R4, R5, R8 and R9 each independently represent mono, di, tri, tetra substitutions, or no substitution;
wherein R3, R6 and R7 each independently represent mono, di, tri substitutions, or no substitution;
wherein m is 0;
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 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 acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein Z1, Z2, Z3 and Z4 are each independently selected from the group consisting of N, CH and CD.

12. The first device of claim 11, wherein the organic layer is an emissive layer and the compound of the formula I is a host.

13. The first device of claim 11, wherein the organic layer further comprises a phosphorescent emissive dopant.

14. The first device of claim 13, wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:









wherein Ra, Rb, Rc, and Rd may represent mono, di, tri, or tetra substitution, or no substitution;
wherein Ra, Rb, Rc, and Rd are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and
wherein two adjacent substituents of Ra, Rb, Rc, and Rd are optionally joined to form a fused ring or form a multidentate ligand.

15. The first device of claim 11, wherein the organic layer is a blocking layer and the compound of formula I is a blocking material in the organic layer.

16. The first device of claim 11, wherein the first device is a consumer product.

17. The first device of claim 11, wherein the first device is an organic light-emitting device.

18. The first device of claim 11, wherein the first device comprises a lighting panel.

19. The first device of claim 11, wherein the compound of formula I is:

20. A formulation comprising the compound of claim 1.