Patent Application
20150236268
The present invention relates to novel diarylamino phenyl carbazole compounds. In particular, these compounds are useful as materials that can be incorporated into a secondary hole transport layer in OLED devices.
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 one aspect, a compound having the formula I is provided:
In the compound of Formula I, Ar1 and Ar2 are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and R1, R2, R3 and R4 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.
In one aspect. R3 and R4 are independently selected from the group consisting of alkyl, heteroalkyl, arylalkyl, aryl, and heteroaryl. In one aspect, R3 and R4 are hydrogen or deuterium.
In one aspect, the compound has the formula:
In one aspect, Ar1 and Ar2 are independently selected from the group consisting of:
In one aspect, Ar1 and Ar2 are independently selected from the group consisting of:
In one aspect, Ar1 and Ar2 are independently selected from the group consisting of:
In one aspect, X is O or S. In one aspect, Ar1 and Ar2 are aryl.
In one aspect, the compound is selected from the group consisting of:
In one aspect, a first device is provided. The first device comprises an organic light emitting device, further comprising: an anode, a cathode, a hole injection layer disposed between the anode and the emissive layer, a first hole transport layer disposed between the hole injection layer and the emissive layer, and a second hole transport layer disposed between the first hole transport layer and the emissive layer, and wherein the second hole transport layer comprises a compound of formula:
In the compound of Formula II, Ar1, Ar2, and Ar5 are independently selected from the group consisting of aryl and heteroaryl and R3 and R4 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.
In one aspect, the compound has the formula:
wherein X is selected from the group consisting of O, S, and Se, wherein R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and wherein R1 and R2 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.
In one aspect, the second hole transport layer is disposed adjacent to the first hole transport layer. In one aspect, the first hole transport layer is thicker than the second hole transport layer. In one aspect, the first hole transport layer comprises a compound with the formula:
wherein Ara, Arb, Arc and Ard are independently selected from the group consisting of aryl and heteroaryl.
In one aspect, the triplet energy of the compound of Formula II is higher than the emission energy of the emissive layer.
In one aspect, Ar1, Ar2 and Ar5 are independently selected from the group consisting of:
In one aspect, Ar1 and Ar2 are independently selected from the group consisting of:
In one aspect, Ar1 and Ar2 are independently selected from the group consisting of:
In one aspect, the first device further comprises a first dopant material that is an emissive dopant comprising 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 and 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 one aspect, the first device is a consumer product. In one aspect, the first device is an organic light-emitting device. In one aspect, the first device comprises a lighting panel. In one aspect, a first device comprising an organic light emitting device, further comprising an anode, a cathode, a first organic layer disposed between the anode and the cathode, and wherein the first organic layer comprises a compound of formula:
In the compound of Formula I, Ar1 and Ar2 are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and R1, R2, R3 and R4 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.
In one aspect, the first organic layer is an emissive layer. In one aspect, the emissive layer is a phosphorescent emissive layer.
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.
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.
The simple layered structure illustrated in
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
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution 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, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.
In one embodiment, a compound having the formula I is provided:
In the compound of Formula I, Ar1 and Ar2 are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and R1, R2, R3 and R4 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.
In one embodiment, R3 and R4 are independently selected from the group consisting of alkyl, heteroalkyl, arylalkyl, aryl, and heteroaryl. In one embodiment, R3 and R4 are hydrogen or deuterium.
In one embodiment, the compound has the formula:
In one embodiment, Ar1 and Ar2 are independently selected from the group consisting of:
In one embodiment, Ar1 and Ar2 are independently selected from the group consisting of:
In one embodiment, Ar1 and Ar2 are independently selected from the group consisting of:
In one embodiment, X is O or S. In one embodiment, Ar1 and Ar2 are aryl.
In one embodiment, the compound is selected from the group consisting of:
In some embodiments, the compounds are selected from the group consisting of Compound 1-Compound 1183 as depicted in Table 1. The list of substituents in Table 1 is as follows:
The subscript “x” in Arx depends on whether the group is Ar1, Ar2, or Ar5.
In one embodiment, a first device is provided. The first device comprises an organic light emitting device, further comprising: an anode, a cathode, a hole injection layer disposed between the anode and the emissive layer, a first hole transport layer disposed between the hole injection layer and the emissive layer, and a second hole transport layer disposed between the first hole transport layer and the emissive layer, and wherein the second hole transport layer comprises a compound of formula:
In the compound of Formula II, Ar1, Ar2, and Ar5 are independently selected from the group consisting of aryl and heteroaryl and R3 and R4 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.
As used herein, a hole transporting layer (HTL) in an OLED can be disposed between the and anode and the emissive layer. It is preferred that the HTL is relatively hole conductive, which helps avoid high operating voltage. In order to achieve high hole conductivity, high hole mobility materials are used. These materials are usually triarylamine compounds. These compounds may have HOMO/LUMO levels and/or triplet energy which are not compatible with the emissive layer for optimum device performance and lifetime. On the other hand, in order to have an HTL with more compatible HOMO/LUMO levels and/or triplet energy, hole mobility may be compromised.
In order to achieve a low voltage, higher device performance and lifetime device, the introduction of a secondary hole transporting layer, in addition to the primary hole transporting layer has been demonstrated and shown to be effective. The primary hole transporting layer is largely responsible for hole transport. The secondary hole transporting layer, sandwiched between the primary hole transporting layer and the emissive layer, functions as a bridging layer. The thickness of the secondary hole transport layer is preferably low in order to not significantly increase the operating voltage. However, the hole injection from the secondary hole transporting layer to the emissive layer, charge confinement and exciton confinement between the secondary hole transporting layer and the emissive layer are controlled by the energy levels and single/triplet energy of the secondary hole transporting layer. Since the secondary hole transporting layer thickness is low, there is relatively little concern about the hole mobility. This allows for a higher flexibility in the design of materials with appropriate energy levels and single/triplet energy to function well with the emissive layer.
It has surprisingly been discovered that compounds of Formula I and Formula II are useful materials in the secondary hole transporting layer. In the compounds of Formula I, the most electron rich portion of the molecule is the N(Ar1)(Ar2) group. Without being bound by theory, this part is believed to be mostly responsible for the hole transport.
The carbazole-N—Ar5 moiety may be less electron rich and may provide a relatively accessible LUMO level and r-conjugation to stabilize radical anions if the material is reduced. In particular, Ar5 is preferably a high triplet fused-ring aromatic as disclosed herein. In some embodiments, Ar5 can be triphenylene or heteroaromatic group such as dibenzofuran, dibenzothiophene and dibenzoselenophene. It has been discovered that the aforementioned substitution pattern for Ar1, Ar2, and Ar5 can render compounds with high triplet energy and significant charge stabilization.
In one embodiment, the compound has the formula:
wherein X is selected from the group consisting of O, S, and Se, wherein R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and wherein R1 and R2 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.
In one embodiment, the second hole transport layer is disposed adjacent to the first hole transport layer. By “adjacent” it is meant that the second hole transport layer is physically in contact with the first hole transport layer. In one embodiment, the first hole transport layer is thicker than the second hole transport layer. In one embodiment, the first hole transport layer comprises a compound with the formula:
wherein Ara, Arb, Arc and Ard are independently selected from the group consisting of aryl and heteroaryl.
In one embodiment, the triplet energy of the compound of Formula II is higher than the emission energy of the emissive layer.
In one embodiment, Ar1, Ar2 and Ar5 are independently selected from the group consisting of:
In one embodiment, Ar1 and Ar2 are independently selected from the group consisting of:
In one embodiment, Ar1 and Ar2 are independently selected from the group consisting of:
In one embodiment, the first device further comprises a first dopant material that is an emissive dopant comprising 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 and 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 one embodiment, the first device is a consumer product. In one embodiment, the first device is an organic light-emitting device. In one embodiment, the first device comprises a lighting panel. In one embodiment, a first device comprising an organic light emitting device, further comprising an anode, a cathode, a first organic layer disposed between the anode and the cathode, and wherein the first organic layer comprises a compound of formula:
In the compound of Formula I, Ar1 and Ar2 are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R1 and R2 independently represent mono, di, tri, tetra substitution, or no substitution, and R1, R2, R3 and R4 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.
In one embodiment, the first organic layer is an emissive layer. In one embodiment, the emissive layer is a phosphorescent emissive layer.
Device Examples
All OLED device examples were fabricated by high vacuum (<10−7 Torr) thermal evaporation (VTE). The anode electrode is ˜800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) and a moisture getter was incorporated inside the package.
The organic stack of the Device Examples in Table 2 consists of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as the hole injection layer (HIL), 500 Å of NPD as the primary hole transporting layer (HTL), 50 Å of the secondary hole transporting layer, 300 Å of Compound A doped with 10% or 12% of phosphorescent dopant Compound B as the emissive layer (EML), 50 Å of Compound A as the ETL2 and 450 Å of Alq3 as the ETL1.
Comparative Example 1 was fabricated in the same way except that there was no secondary hole transporting layer, and the thickness of the primary hole transporting layer was increased to 550 Å to match the combined thickness of the primary and secondary hole transporting layers in the Device Examples.
The structures of the aforementioned device components are as follows:
Device Examples 1-3 are the same as Comparative Device Example 1 except for the presence of the secondary HTL in former and the absence of the secondary HTL in latter. Device Examples 1-3 have Compounds 113, 178 and 182 respectively as the secondary HTL. The efficiencies of Device Examples 1-3 are higher (EQE=20.7-20.9%) than the efficiency of Comparative Device Example 1 (EQE=18.6%). The operation lifetimes of Device Examples 2 and 3 are remarkably high. The LT80, the time required for the initial luminance (L0) to drop to 80% of its initial value, at a constant current density of 40 mA/cm2, is ˜420 h, compared to 290 h of Comparative Device Example 1. Without being bound by theory, the improved efficiency and lifetime when Compounds 178 and 182 are used as the secondary HTL may be due to the high triplet energy, providing improved exciton confinement; the presence of a dibenzothiophene or triphenylene group, providing a high triplet, charge stabilization moiety; and a sufficiently shallow HOMO level (Compound 178 HOMO=−5.23 eV, Compound 182 HOMO=−5.21 eV, NPD HOMO=−5.17 eV) for hole transport.
Although hole conductivity may be reduced in compounds of Formula I or Formula II with respect to traditionally used triarylamine compounds such as NPD, compounds of Formula I and Formula II that bear substituents such as
(Group 1) at the Ar1 and Ar2 positions have better hole mobility that compounds bearing substituents such as
(Group 2) at these same positions because the latter group of substituents, deepens the HOMO levels, which causes a larger increase in hole conductivity. Additionally, although device lifetimes for a given thickness of the secondary HTL are sometimes reduced for compounds bearing Group 2 substituents compared with Group 1 substituents, this difference can be mitigated by decreasing the thickness of the secondary HTL.
The HOMO and LUMO levels and triplet energy are summarized in Table 3. The LT80 of Device Example 1 with Compound 113 as the secondary HTL is 200 h, less stable than Device Example 1 (422 h) with Compound 178 as the secondary HTL. The difference between Compound 113 and Compound 178 is the N(Ar1)(Ar2) group. In general, if the N is connected to a dibenzofuran or dibenzothiphene group, the HOMO gets deeper (Compound 1 HOMO=−5.31 eV, NPD HOMO=−5.17 eV) and hole conductivity may be reduced. This may lead to shorter device operation lifetime if the hole conductivity of the secondary HTL is not high enough, even though its thickness is kept low.
* By solution electrochemistry using ferrocene as the standard
#By DTF/B3LYP/6-31g(d) optimized geometry
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.
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 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 a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
k is an integer from 1 to 20; X1 to X8 is C (including CH) or N; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:
M is a metal, having an atomic weight greater than 40; (Y1-Y2) is a bidentate ligand, Y1 and Y2 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y1-Y2) is a 2-phenylpyridine derivative.
In another aspect, (Y1-Y2) is a carbene ligand.
In another aspect, M is selected from Ir, Pt, Os, and Zn.
In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
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 energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
M is a metal; (Y3-Y4) is a bidentate ligand, Y3 and Y4 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
(O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, M is selected from Ir and Pt.
In a further aspect, (Y3-Y4) is a carbene ligand.
Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, host compound contains at least one of the following groups in the molecule:
R1 to R7 is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
k is an integer from 0 to 20.
X1 to X8 is selected from C (including CH) or N.
Z1 and Z2 is selected from NR1, O, or S.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.
Electron transport layer (ETL) may include a material capable of transporting electrons.
Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
R1 is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.
Ar1 to Ar3 has the similar definition as Ar's mentioned above.
k is an integer from 0 to 20.
X1 to X8 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated.
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 4 below. Table 4 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.
and
and its derivatives
Chemical abbreviations used throughout this document are as follows: Cy is cyclohexyl, dba is dibenzylideneacetone. EtOAc is ethyl acetate, DME is dimethoxyethane, dppe is 1,2-bis(diphenylphosphino)ethane, THF is tetrahydrofuran, DMF is dimethylformamide, DCM is dichloromethane, S-Phos is dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine, Tf is trifluoromethylsulfonate. Unless specified otherwise, references to degassing a particular solvent refer to saturating the solvent sufficiently with dry nitrogen gas (by bubbling it in the solvent) to substantially remove gaseous oxygen from the solvent.
Toluene (125 mL) was bubbled with nitrogen gas for 15 minutes, and subsequently 1,1′-Bis(diphenylphosphino)ferrocene (0.2 g, 0.4 mmol) and Pd2(dba)3 (0.1 g, 0.1 mmol) were added. The mixture was bubbled with nitrogen gas for 15 minutes, then N-phenyldibenzo[b,d]thiophen-4-amine (3.2 g, 11.6 mmol), 1-bromo-4-iodobenzene (4.5 g, 15.9 mmol), NaOtBu (1.5 g, 15.6 mmol) were added. The mixture was bubbled with nitrogen gas for 15 minutes and refluxed for 12 hours. After cooling, the reaction mixture was filtered through a silica pad and washed with 50% CH2Cl2/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 10-15% CH2Cl2/hexane to afford N-(4-bromophenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (4.0 g, 80% yield) as a white solid.
To a solution of N-(4-bromophenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (8.3 g, 19.3 mmol) in 1,4-dioxane (250 mL) was added bis(pinacolato)diboron (7.6 g, 29.9 mmol), KOAc (3.9 g, 39.8 mmol), and the solution was bubbled with nitrogen for 15 minutes. Pd(dppf)Cl2.CH2Cl2 (0.5 g, 0.6 mmol) was then added to the solution, and the reaction mixture was bubbled with nitrogen for 15 minutes. The resultant mixture was refluxed for 12 hours. After cooling, H2O (1 mL) was added and stirred for 15 min. The reaction mixture was filtered through a silica pad and washed with 75% CH2Cl2/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 25-40% CH2Cl2/hexane to afford N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine (5.9 g, 64% yield) as a white solid.
To a solution of N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine (5.9 g, 12.4 mmol), 3-bromocarbazole (3.5 g, 14.2 mmol), K2CO3 (16.6 g, 120.0 mmol) in toluene (150 mL), water (50 mL) and EtOH (50 mL) was bubbled for 30 min. Pd(PPh3)4 (0.4 g, 0.4 mmol) was added. The mixture was bubbled for 15 min. The resultant mixture was refluxed for 12 h. After cooling, the reaction mixture was extracted by CH2Cl2 and dried by MgSO4. The solvent was removed in vacuo and the residue was purified by flash chromatography using 25-50% CH2Cl2/hexane to afford N-(4-(9H-carbazol-3-yl)phenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (5.8 g, 91% yield) as a white solid.
Xylene (175 mL) was bubbled with nitrogen for 15 minutes, followed by addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2.3 g, 5.6 mmol) and Pd2(dba)3 (1.3 g, 1.4 mmol). The mixture was again bubbled nitrogen for 15 minutes, then N-(4-(9H-carbazol-3-yl)phenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (3.4 g, 6.6 mmol), 4-iododibenzothiophene (3.3 g, 10.6 mmol), sodium tert-butoxide (1.4 g, 14.0 mmol) were added. The mixture was bubbled with nitrogen for 15 minutes and refluxed for 12 hours. After cooling, the reaction mixture was filtered through a silica pad and washed with 80% CH2Cl2/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 20-35% CH2Cl2/hexane to afford Compound 113 (2.9 g, 63% yield) as a white solid.
N-bromosuccinimide (17.8 g, 0.1 mol) in 50 mL of DMF was added slowly to diphenylamine (8.46 g, 0.05 mol) in 50 mL of DMF at 0° C. in 30 minutes. The reaction was allowed to warm to room temperature and stir overnight. The white precipitate was filtered and air dried, and 16 g of product was collected.
Bis(4-bromophenyl)amine (4.0 g, 12.3 mmol) and phenylboronic acid (4.0 g, 32.7 mmol) were mixed in 250 mL of toluene and 60 mL of ethanol. The solution was bubbled with nitrogen while stirring for 15 minutes. Pd(PPh3)4 (1.4 g, 1.23 mmol) and K3PO4 (13.5 g, 64 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through filter paper and the solvent was then evaporated. The solid was redissolved in nitrogen-purged hot toluene and was filtered through a Celite®/silica pad when the solution was still hot. The solvent was then evaporated. The white crystalline solid was washed by hexane and air dried to obtain 3.8 g of product.
Di([1,1′-biphenyl]-4-yl)amine (3.5 g, 10.9 mmol) and 1-bromo-4-iodobenzene (6.0 g, 21.3 mmol) were mixed in 300 mL of dry toluene. The solution was bubbled with nitrogen while stirring for 15 minutes. Pd(OAc)2 (36 mg, 0.16 mmol), triphenylphosphine (0.16 g, 0.6 mmol) and sodium t-butoxide (2.0 g, 20.8 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 3.9 g of product.
Carbazole (0.62 g, 3.67 mmol) and 4-iododibenzothiophene (1.2 g, 3.87 mmol) were mixed in 70 mL of dry xylene. The solution was bubbled nitrogen while stirring for 15 minutes. Pd2(dba)3 (0.16 g, 0.17 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.24 g, 0.58 mmol) and sodium tert-butoxide (1.0 g, 10.4 mmol) were added in sequence. The mixture was heated to reflux for 3 days under nitrogen. After cooling, the reaction mixture was filtered through a Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 0.64 g of product.
N-bromosuccinimide (0.31 g, 1.74 mmol) in 5 mL DMF was added slowly to 9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole (0.6 g, 1.72 mmol) in 50 mL of DCM at 0° C. The reaction was allowed to warm to room temp and stirred overnight. The reaction mixture was extracted with DCM and dried over MgSO4 and the solvent was evaporated. The residue was purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 0.45 g of product.
3-bromo-9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole (0.45 g, 1.1 mmol), bis(pinacolato)diboron (0.43 g, 1.4 mmol) and KOAc (0.31 g, 3.1 mmol) were mixed in 150 mL of dry 1,4-dioxane. The solution was bubbled with nitrogen while stirring for 15 minutes, then Pd(dppf)Cl2.CH2Cl2 (26 mg, 0.03 mmol) was added. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (3:7, v/v) as the eluent to obtain 0.4 g of product.
N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1′-biphenyl]-4-amine (2.5 g, 5.25 mmol), and 9-(dibenzo[b,d]thiophen-4-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (2.64 g, 5.58 mmol) were mixed in 250 mL of toluene and 30 mL of deionized water. The solution was bubbled with nitrogen while stirring for 15 minutes, then Pd2(dba)3 (0.12 g, 0.13 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.21 g, 0.51 mmol) and K3PO4 (3.5 g, 16.5 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. Bromobenzene (1 mL) was added to the reaction mixture and the reaction was further refluxed for 4 hours. After cooling, the reaction mixture was filtered through a Celite®/silica pad and the solvent was then evaporated. Compound 178 (2.4 g) was collected and purified by recrystallization from 20 mL of degassed toluene.
To a stirred solution of Pd2(dba)3 (0.52 g, 0.57 mmol) in o-xylene (140 mL), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.94 g, 2.3 mmol) was added and degassed with nitrogen for 15 minutes. Carbazole (5.33 g, 31.9 mmol) and 2-bromotriphenylene (7.0 g, 22.7 mmol), sodium tert-butoxide (6.57 g, 68.3 mmol) were added and degassed with nitrogen for another 15 minutes. The reaction was refluxed for 2 days. The reaction mixture was filtered through silica, washed with DCM and dried under vacuum. Silica gel chromatography with 10% DCM/hexane, yielded 4.98 g of a while solid (56%) as the product.
To a stirred solution of 9-(triphenylen-2-yl)-9H-carbazole (4.7 g, 11.9 mmol) in DMF (24 mL) at 0° C. under N2, NBS (N-bromosuccinimide) (2.1 g, 11.9 mmol) in DMF (24 mL) was added dropwise. After the completion of addition, the reaction mixture was warmed to room temperature overnight with vigorous stirring. The reaction mixture was precipitated with water and the solid was filtered. The pale grey solid was re-dissolved in a small amount of THF, added on a silica plug and flushed with 30% DCM/hexane. The filtrate was dried under vacuum and the white solid was used without further purification (5.5 g, 98%).
To a stirred solution of 3-bromo-9-(triphenylen-2-yl)-9H-carbazole (3.0 g, 6.4 mmol) in 1,4-dioxane (90 mL), bis(pinacolato)diboron (2.4 g, 9.5 mmol) and KOAc (1.8 g, 19.1 mmol) were added and degassed with nitrogen for 15 min, then Pd(dppf)Cl2.CH2Cl2 (0.14 g, 0.2 mmol) was added and the mixture was degassed with nitrogen for another 15 minutes. The solution was refluxed for 2 days. After cooling to room temperature, water (1 mL) was added and the reaction mixture was stirred for 30 minutes. The reaction mixture was filtered through silica and dried under vacuum. The solid was column chromatographed with 20-50% DCM/hexane, yielding 2.0 g of a while solid (61%) as the product.
To a stirred solution of N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1′-biphenyl]-4-amine (0.9 g, 1.9 mmol) in toluene (29 mL) and water (2.9 mL), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(triphenylen-2-yl)-9H-carbazole (1.0 g, 1.9 mmol) and K3PO4 (2.4 g, 11.3 mmol) were added and the mixture was degassed with nitrogen for 15 minutes, then Pd2(dba)3 (86 mg, 0.09 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.16 g, 0.38 mmol) were added and degassed with nitrogen for another 15 minutes. The mixture was refluxed overnight. After cooling to room temperature, the reaction mixture was filtered through silica, washed with DCM and dried under vacuum. It was column chromatographed with 20-50% DCM/hexane yielding 1.03 g of a while solid (69%) as Compound 182.
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.
This application is a continuation application of U.S. patent application Ser. No. 13/421,489, filed Mar. 15, 2012, the disclosure of which is expressly incorporated herein by reference in its entirety.
The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and 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.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13421489 | Mar 2012 | US |
| Child | 14705103 | US |
