Heteroleptic iridium carbene complexes and light emitting device using them

This application claims the priority of US Patent Application No. 61 / 494,667 filed June 8, 2011, the entire disclosure of which is incorporated herein by reference.

The claimed invention may be in the interest of one or more of the following parties to the university-company joint research agreement: University of Michigan, Princeton University, University of Southern California, and one or more of the directors of the Universal Display Corporation: And / or related to. The contract came into effect before the date on which the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of the contract.

The present invention relates to a novel heteroreptic iridium carbene complex. In particular, these iridium complexes are phosphorescent and are useful as illuminants in OLEDs.

Optoelectronic devices that utilize organic materials are becoming increasingly desirable for a number of reasons. Since many of the materials used to make such devices are relatively inexpensive, organic optoelectronic devices have the potential for cost advantage over inorganic devices. In addition, the inherent properties of organic materials, such as flexibility, can make the material well suited for specific applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (OLEDs), organic light transistors, organic photovoltaic cells and photodetectors. For OLEDs, organic materials can have performance advantages over traditional materials. For example, the wavelength at which the organic light emitting layer emits light can generally be easily adjusted with a suitable dopant.

OLEDs utilize thin organic films that emit light when a voltage is applied to the entire device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting. Several OLED materials and configurations are described in Patent Document 1, Patent Document 2 and Patent Document 3, which are incorporated herein by reference in their entirety.

One use for phosphorescent luminescent molecules is in full color displays. Industry standards for such displays require pixels that are adapted to emit a particular color, called a "saturated" color. In particular, these standards require saturated red, green and blue pixels. Color can be measured using CIE coordinates well known in the art.

An example of a green luminescent molecule has the following structure:<chemistry num="1"><img file="JP6869293B2_D0001.tif" /></chemistry>Has, Ir (ppy)₃It is a tris (2-phenylpyridine) iridium displayed as.

In this drawing and later in the drawings herein, we describe the coordination bond from nitrogen to a metal (here Ir) as a straight line.

As used herein, the term "organic" includes polymeric and small molecule organic materials that can be used to make organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" may actually be quite large. Small molecules can contain repeating units in some situations. For example, using a long-chain alkyl group as a substituent does not exclude the molecule from the "small molecule" class. Small molecules may be incorporated into the polymer, for example as a pendant group on the polymer backbone or as part of the backbone. Small molecules can also serve as the core part of a dendrimer consisting of a series of chemical shells built on top of the core part. The core portion of the dendrimer may be a fluorescent or phosphorescent small molecule illuminant. Dendrimers can be "small molecules" and all dendrimers currently in use in the field of OLEDs are considered to be small molecules.

As used herein, "top" means the furthest part from the substrate, while "bottom" means the most recent part of the substrate. When the first layer is described as "located on top of" the second layer, the first layer is located farther from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, the cathode can be described as "located above" the anode, even though there are various organic layers in between.

As used herein, "solution processable" can be dissolved, dispersed or transported in a liquid medium, either in solution or suspension form, and / or deposited from that medium. It means that it can be done.

A ligand can be referred to as "photoactive" if the ligand is believed to contribute directly to the photoactive properties of the light emitting material. A ligand can be referred to as an "auxiliary" if it is believed that the ligand does not contribute to the photoactive properties of the light emitting material, whereas the co-ligand has the properties of a photoactive ligand. Can be changed.

As used herein, the first "highest occupied molecular orbital" (HOMO) or "lowest empty molecular orbital" (LUMO) energy level is, as will be generally understood by those skilled in the art. If the first energy level is close to the vacuum energy level, then the second HOMO or LUMO energy level is "greater than" or "higher". The higher HOMO energy level corresponds to an IP with a smaller absolute value (less negative IP) because the ionization potential (IP) is measured as negative energy compared to the vacuum level. Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) (less negative EA) with a smaller absolute value. In a conventional energy level diagram with a vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears to be closer to the top of such a figure than the "lower" HOMO or LUMO energy level.

As used herein, as will be generally understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is "more than" the second work function. Also larger "or" higher than ". This means that the "higher" work function is even more negative, as the work function is generally measured as a negative number compared to the vacuum level. In a traditional energy level diagram with a vacuum level at the top, the "higher" work function is illustrated as being far downward from the vacuum level. Therefore, the definitions of HOMO and LUMO energy levels follow a convention different from the work function.

Further details about OLEDs and the definitions described above can be found in Patent Document 4, which is incorporated herein by reference in its entirety.

Compounds comprising a heteroreptic iridium complex having the formula I below are provided.<chemistry num="2"><img file="JP6869293B2_D0002.tif" /></chemistry>In the compound of formula I, R₃, R₄, And R₁₀Indicates that it is mono, di, tri, tetra-substituted or unsubstituted, and R₇Halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, It is selected from the group consisting of isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. R₁, R₃, R₄, R₅, R₆, R₈, R₉, And R₁₀Are independent 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. R₅And R₉Each has a molecular weight of more than 15.5 g / mol, and any two adjacent substituents may be bonded to form a ring or may be further substituted. n is 1 or 2.

In one embodiment, n is 2. In one embodiment, n is 1. In one embodiment, R₅And R₉Is an alkyl or cycloalkyl having at least two carbon atoms.

In one embodiment, R₅And R₉Independently, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1, Selected from the group consisting of 2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, each group may be partially or completely dehydrogenated.

In one embodiment, R₅And R₉Is aryl or heteroaryl. In one embodiment, R₇Is aryl or heteroaryl. In one embodiment, R₇Is phenyl.

In one embodiment, R₁Is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In one embodiment, R₁~ R₁₀At least one of them contains deuterium.

In one embodiment, the compound has Formula II below.<chemistry num="3"><img file="JP6869293B2_D0003.tif" /></chemistry>In the formula, Y is O, S, NR₁₂, And CR₁₂R₁₃Selected from the group consisting of. R₁₁Represents mono, di, tri, tetra-substituted or unsubstituted. R₁₁, R₁₂, And R₁₃Are independent 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.

In one embodiment, the compound is selected from the group consisting of:<chemistry num="4"><img file="JP6869293B2_D0004.tif" /></chemistry><chemistry num="5"><img file="JP6869293B2_D0005.tif" /></chemistry><chemistry num="6"><img file="JP6869293B2_D0006.tif" /></chemistry><chemistry num="7"><img file="JP6869293B2_D0007.tif" /></chemistry>In the formula, X is O or S and Y is O or S. R₅And R₉Independently, methyl-d3, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1- Selected from the group consisting of dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof, each group is partially or completely dehydrogenated. May be good. R₁And R₇Independently, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl , 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof. Selected from the group, each group may be partially or completely dehydrolated.

In one embodiment, the compound is selected from the group consisting of compounds 1 to 61.

In one embodiment, a first device is provided. The first device comprises an organic light emitting device, further comprising an anode, a cathode, and an organic layer comprising the compound having the formula I below, located between the anode and the cathode.<chemistry num="8"><img file="JP6869293B2_D0008.tif" /></chemistry>In the compound of formula I, R₃, R₄, And R₁₀Indicates that it is mono, di, tri, tetra-substituted or unsubstituted, and R₇Halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, It is selected from the group consisting of isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. R₁, R₃, R₄, R₅, R₆, R₈, R₉, And R₁₀Are independent 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. R₅And R₉Each has a molecular weight of more than 15.5 g / mol, and any two adjacent substituents may be bonded to form a ring or may be further substituted. n is 1 or 2.

In one embodiment, the organic layer is a light emitting layer and the compound is a light emitting dopant. In one embodiment, the organic layer further comprises a host.

In one embodiment, the host is at least a chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. Including one.

In one embodiment, the host is a metal complex. In one embodiment, the host is a metal carbene complex.

In one embodiment, the metal carbene complex is selected from the group consisting of:<chemistry num="9"><img file="JP6869293B2_D0009.tif" /></chemistry><chemistry num="10"><img file="JP6869293B2_D0010.tif" /></chemistry>

In one embodiment, the device further comprises a second organic layer, which is a non-light emitting layer, between the anode and the light emitting layer, in which the material in the second organic layer is a metal carbene complex.

In one embodiment, the device further comprises a third organic layer, which is a non-light emitting layer, between the cathode and the light emitting layer, the material of which is a metal carbene complex.

In one embodiment, the device further comprises a second organic layer that is a non-emissive layer, the compound of formula I being the material in the second organic layer.

In one embodiment, the second organic layer is the hole transport layer and the compound of formula I is the transport material in the second organic layer.

In one embodiment, the second organic layer is the blocking layer and the compound of formula I is the blocking material in the second organic layer.

In one embodiment, the first device is an organic light emitting device.

In one embodiment, the first device is a consumer product.

In one embodiment, the first device comprises a lighting panel.

<figref num="1">FIG. 1 shows an organic light emitting device.</figref>

<figref num="2">FIG. 2 represents an inversely structured organic light emitting device without a separate electron transport layer.</figref>

<figref num="3">FIG. 3 shows a compound of formula I.</figref>

Generally, the OLED contains at least one organic layer located between the anode and the cathode and electrically connected to them. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer (s). The injected holes and electrons move to the back-charged electrodes, respectively. When electrons and holes are localized on the same molecule, "excitons", which are localized electron-hole pairs with an excited energy state, are formed. Light is emitted via a photoelectron emission mechanism when excitons are relaxed. In some cases, excitons can be localized on excimers or excimers. Non-radiation mechanisms such as thermal relaxation may occur, but are generally considered undesirable.

Early OLEDs used luminescent molecules ("fluorescence") that emit light from their singlet state, for example, as disclosed in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence generally occurs in a time frame of less than 10 nanoseconds.

Most recently, OLEDs with luminescent materials ("phosphorescent") that emit light from the triplet state have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices," Volumes 395, 151-154, 1998; ("Baldo-I") and Baldo et al., "Very high-efficiency green organic light," which are incorporated by reference in their entirety. emitting devices based on electrophosphorescence ", Appl.Phys.Lett., Vol. 75, No. 3, 4-6 (1999) (" Baldo-II "). Phosphorescence is described in more detail in US Pat. No. 7,279,704, paragraphs 5-6, incorporated by reference.

FIG. 1 shows the organic light emitting device 100. The figure is not always at a constant scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, and a protective layer 155. , Cathode 160 and barrier layer 170 may be included. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be made by depositing the described layers in sequence. The properties and functions of these various layers and material examples are described in more detail in US 7,279,704, tiers 6-10, incorporated by reference.

Further examples are available for each of these layers. For example, flexible and transparent substrate-anode combinations are disclosed in US Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is F to m-MTDATA at a molar ratio of 50: 1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety.₄-It is doped with TCNQ. Examples of luminescent and host materials are disclosed in US Pat. No. 6,303,238 of Thompson et al., Incorporated in its entirety by reference. An example of an n-doped electron transport layer is BPhen Li-doped in a 1: 1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Is. US Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, provide a composite cathode with a thin layer of metal such as Mg: Ag with a clear, conductive, sputter-deposited ITO layer overlying. An example of a cathode including the cathode is disclosed. The theory and use of blocking layers is described in more detail in US Pat. No. 6,097,147 and US Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entirety. An example of an injection layer is provided in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer can be found in US Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED200. The device includes a substrate 210, a cathode 215, a light emitting layer 220, a hole transport layer 225, and an anode 230. The device 200 can be made by depositing the described layers in sequence. The device 200 is referred to as the "inverted" OLED because the most common OLED configuration has a cathode located above the anode and the device 200 has a cathode 215 located below the anode 230. There is. Materials similar to those described for device 100 may be used in the corresponding layers of device 200. FIG. 2 provides an example of how several layers can be omitted from the structure of device 100.

It is understood that the simple layered structures illustrated in FIGS. 1 and 2 are provided as non-limiting examples and that embodiments of the present invention may be used in connection with a wide variety of other structures. Will be done. The particular materials and structures described are exemplary in nature and other materials and structures may be used. A functional OLED can be realized by combining the various layers described in various ways, or the layers can be omitted altogether 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. Many of the examples provided herein describe the various layers as containing a single material, but use a combination of materials, such as a mixture of hosts and dopants, or more generally a mixture. It is understood that you can do it. Further, the layer may have various sub-layers. The names given to the various layers herein are not intended to be strictly limited. For example, in device 200, the hole transport layer 225 can transport holes, inject holes into the light emitting layer 220, and be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED can be described as having an "organic layer" located between the cathode and the anode. The organic layer may include a single layer, or may further include multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Using structures and materials not specifically described, such as OLEDs (PLEDs) composed of polymeric materials, such as those disclosed in Friend et al., US Pat. No. 5,247,190, which is incorporated by reference in its entirety. May be good. As a further example, OLEDs with a single organic layer can be used. OLEDs may be stacked, for example, as described in US Pat. No. 5,707,745 of Forrest et al., Incorporated in its entirety by reference. The OLED structure may deviate from the simple layered structure illustrated in Figures 1 and 2. For example, the substrate is incorporated by reference in its entirety, with a mesa structure as described in US Pat. No. 6,091,195 by Forrest et al. And / or a recessed structure as described in US Pat. No. 5,834,893 by Bulovic et al. Etc., may include angled reflective surfaces to improve out-coupling.

Unless otherwise specified, any of the layers of the various embodiments can be deposited by any suitable method. For organic layers, preferred methods are the thermal deposition, inkjet, and US patents of Forrest et al., Incorporating the whole by reference, such as those described in US Pat. Nos. 6,013,982 and 6,087,196. Organic vapor deposition (OVPD), such as those described in Nos. 6,337,102, and organic vapor phase jet printing (OVJP), such as those described in U.S. Patent Application No. 10 / 233,470, which is incorporated by reference in its entirety. ) Includes deposition. Other suitable deposition methods include spin coating and other solution-based processes. The solution-based process is preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal deposition. Preferred patterning methods are masks such as those described in US Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety, deposits via cold pressure welding, and deposit methods such as inkjet and OVJD. Includes crab-related patterning. Other methods may be used. The material to be deposited can be modified to be compatible with the particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or non-branched and preferably contain at least 3 carbons are used in small molecules to enhance their ability to undergo solution processing. Can be used. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being the preferred range. Materials with an asymmetric structure may have better solution processability than those with a symmetric structure, as asymmetric materials may be less prone to recrystallization. Dendrimer substituents can be used to enhance the ability of small molecules to undergo solution processing.

Devices made according to embodiments of the present invention may further include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layer from damaging exposure to harmful species in the environment, including moisture, vapor and / or gas. The barrier layer can be deposited on the substrate, above, below or next to the electrodes, or on any other part of the device, including the edges. The barrier layer may include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having a polyphase. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic and / or organic compounds. Preferred barrier layers are incorporated herein by reference in their entirety, as described in US Pat. No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and PCT / US 2009/042829. Includes a mixture of polymeric and non-polymeric materials. To be considered a "mixture", the polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric to non-polymeric materials can be in the range of 95: 5 to 5:95. Polymeric and non-polymeric materials can be made from the same precursor material. In one example, a mixture of polymeric and non-polymeric materials consists essentially of polymeric and inorganic silicon.

Devices made according to embodiments of the present invention include flat panel displays, computer monitors, televisions, bulletin boards, indoor or outdoor lighting and / or signal transmission lights, head-up displays, fully transparent displays, flexible displays, laser printers, etc. Incorporated into a wide variety of consumer products including phones, mobile phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcoders, finder, microdisplays, cars, large walls, theater or stadium screens, or signs. It can be. Various control mechanisms, including passive and active matrices, can be used to control devices made in accordance with the present invention. Many devices are intended for use within a temperature range that is comfortable for humans, such as 18 to 30 degrees Celsius, more preferably room temperature (20 to 25 degrees Celsius).

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 use the material and structure. More generally, organic devices such as organic transistors can use the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, allylyl, heterocyclic group, aryl, aromatic group and heteroaryl are known in the art and are incorporated herein by reference to US7,279,704. It is defined in the 31st to 32nd columns of.

Compounds comprising a heteroreptic iridium complex having the formula I below are provided.<chemistry num="11"><img file="JP6869293B2_D0011.tif" /></chemistry>In the compound of formula I, R₃, R₄, And R₁₀Indicates that it is mono, di, tri, tetra-substituted or unsubstituted, and R₇Halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, It is selected from the group consisting of isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. R₁, R₃, R₄, R₅, R₆, R₈, R₉, And R₁₀Are independent 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. R₅And R₉Each has a molecular weight of more than 15.5 g / mol, and any two adjacent substituents may be bonded to form a ring or may be further substituted. n is 1 or 2.

In one embodiment, n is 2. In one embodiment, n is 1. In one embodiment, R₅And R₉Is an alkyl or cycloalkyl having at least two carbon atoms.

In one embodiment, R₅And R₉Independently, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1, Selected from the group consisting of 2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, and cyclohexyl, each group may be partially or completely dehydrogenated.

In some embodiments, R₅And R₉Are preferably at least as large as the isopropyl group. Such groups create a twist in the aryl ring to which they are attached. Without being bound by any theory, this further protects the complex and makes the device using Compound I as the illuminant more stable.

In one embodiment, R₅And R₉Is aryl or heteroaryl. In one embodiment, R₇Is aryl or heteroaryl. In one embodiment, R₇Is phenyl.

In one embodiment, R₁Is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

In one embodiment, R₁~ R₁₀At least one of them contains deuterium.

In one embodiment, the compound has Formula II below.<chemistry num="12"><img file="JP6869293B2_D0012.tif" /></chemistry>In the formula, Y is O, S, NR₁₂, And CR₁₂R₁₃Selected from the group consisting of. R₁₁Represents mono, di, tri, tetra-substituted or unsubstituted. R₁₁, R₁₂, And R₁₃Are independent 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.

In one embodiment, the compound is selected from the group consisting of:<chemistry num="13"><img file="JP6869293B2_D0013.tif" /></chemistry><chemistry num="14"><img file="JP6869293B2_D0014.tif" /></chemistry><chemistry num="15"><img file="JP6869293B2_D0015.tif" /></chemistry><chemistry num="16"><img file="JP6869293B2_D0016.tif" /></chemistry>In the formula, X is O or S and Y is O or S. R₅And R₉Independently, methyl-d3, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1- Selected from the group consisting of dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof, each group is partially or completely dehydrogenated. May be good. R₁And R₇Independently, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl , 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, and combinations thereof. Selected from the group, each group may be partially or completely dehydrolated.

In one embodiment, the compound is selected from the group consisting of:<chemistry num="17"><img file="JP6869293B2_D0017.tif" /></chemistry><chemistry num="18"><img file="JP6869293B2_D0018.tif" /></chemistry><chemistry num="19"><img file="JP6869293B2_D0019.tif" /></chemistry><chemistry num="20"><img file="JP6869293B2_D0020.tif" /></chemistry><chemistry num="21"><img file="JP6869293B2_D0021.tif" /></chemistry><chemistry num="22"><img file="JP6869293B2_D0022.tif" /></chemistry><chemistry num="23"><img file="JP6869293B2_D0023.tif" /></chemistry><chemistry num="24"><img file="JP6869293B2_D0024.tif" /></chemistry><chemistry num="25"><img file="JP6869293B2_D0025.tif" /></chemistry>

In one embodiment, a first device is provided. The first device comprises an organic light emitting device, further comprising an anode, a cathode, and an organic layer comprising the compound having the formula I below, located between the anode and the cathode.<chemistry num="26"><img file="JP6869293B2_D0026.tif" /></chemistry>In the compound of formula I, R₃, R₄, And R₁₀Indicates that it is mono, di, tri, tetra-substituted or unsubstituted, and R₇Halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, It is selected from the group consisting of isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. R₁, R₃, R₄, R₅, R₆, R₈, R₉, And R₁₀Are independent 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. R₅And R₉Each has a molecular weight of more than 15.5 g / mol, and any two adjacent substituents may be bonded to form a ring or may be further substituted. n is 1 or 2.

In one embodiment, the organic layer is a light emitting layer and the compound is a light emitting dopant. In one embodiment, the organic layer further comprises a host.

In one embodiment, the host is a chemical group selected from the group consisting of carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. Includes at least one.

The above-mentioned fragments, namely the name "aza" such as azadibenzofuran, azadibenzothiophene, means that one or more CH groups in each fragment are replaced with nitrogen atoms, and are not limited to, for example. However, azatriphenylene includes both dibenzo [f, h] quinoxaline and dibenzo [f, h] quinoline. One of ordinary skill in the art can easily imagine other nitrogen analogs of the bruise derivatives described above, and it is intended that all such analogs are included by the terms described herein.

In one embodiment, the host is a metal complex. In one embodiment, the host is a metal carbene complex. As used herein, the term "metal carbene complex" means a metal coordination complex containing at least one carbene ligand.

In one embodiment, the metal carbene complex is selected from the group consisting of:<chemistry num="27"><img file="JP6869293B2_D0027.tif" /></chemistry><chemistry num="28"><img file="JP6869293B2_D0028.tif" /></chemistry>

In one embodiment, the device further comprises a second organic layer, which is a non-light emitting layer, between the anode and the light emitting layer, the material of which is a metal carbene complex.

In one embodiment, the device further comprises a third organic layer, which is a non-light emitting layer, between the cathode and the light emitting layer, the material of which is a metal carbene complex.

In one embodiment, the device further comprises a second organic layer that is a non-emissive layer, the compound of formula I being the material in the second organic layer.

In one embodiment, the second organic layer is the hole transport layer and the compound of formula I is the transport material in the second organic layer.

In one embodiment, the second organic layer is the blocking layer and the compound of formula I is the blocking material in the second organic layer.

In one embodiment, the first device is an organic light emitting device.

In one embodiment, the first device is a consumer product.

In one embodiment, the first device comprises a lighting panel.

Device Example

All devices are under high vacuum (&lt;10)^-7Made by thermal thin-film deposition (VTE) in Torr). The anode electrode is 800 Å of indium tin oxide (ITO). The cathode consists of 10 Å of LiF and 1,000 Å of Al. All devices are Nitrogen Glove Boxes (H) immediately after fabrication.₂O and O₂Was sealed in &lt;1 ppm) with a glass lid sealed with an epoxy resin, and a moisture getter was placed in the package.

The organic laminates of the device examples are LG101 (purchased from LG Chem) 100 Å hole injection layer (HIL), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] in order from the ITO surface. 300 Å hole transport layer (HTL) of NPD doped with biphenyl (NPD) or 2% Alq (tris-8-hydroxyquinoline aluminum), 300 Å light emitting layer (EML) doped with 15 wt% compound of formula I in compound H, It consists of a 50 Å blocking layer (BL) and an Alq 350 Å electron transport layer (ETL). The device results and data for these devices are summarized in Tables 1 and 2. As used herein, NPD, Alq, Compound A, and Compound H have the following structures.<chemistry num="29"><img file="JP6869293B2_D0029.tif" /></chemistry>

Table 1 VTE Phosphorescent OLED<tables num="1"><img file="JP6869293B2_D0030.tif" /></tables>

Table 2 VTE device data at 1000 nits<tables num="2"><img file="JP6869293B2_D0031.tif" /></tables>

Table 2 summarizes the device data. Luminous efficiency (LE) and external quantum efficiency (EQE) are measured at 1000 nits and have a lifetime (LT)._80%) Is defined as the time required for the initial brightness of a 1000 nit device to decay to 80% at a constant current density. Compound 1 (compound of formula I) is R₇It has a phenyl substituent at the position of. This substitution significantly improved device performance compared to Comparative Compound A. In a device where the doping% of the luminescent compound (ie, the compound of formula I or Comparative Example) is 15%, both Compound 1 and Compound A have a similar color with a CIE of (0.17, 0.32) and about 15.5. It showed a similar EQE of%. However, compound 1 is LT for 506 hours.₈₀On the other hand, compound A was LT for only 296 hours.₈₀This corresponds to a 70% improvement. Therefore, it is desirable to have the structural characteristics of the compound of the present invention.

Combinations with Other Materials The materials described herein as useful for a particular layer in an organic luminescent device can be used in combination with a wide variety of other materials present in the device. For example, the luminescent dopants disclosed herein can 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 referenced below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and those skilled in the art may use other materials that may be useful in combination. The literature for identification can be easily browsed. HIL / HTL:

The hole injection / transport material 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 injection / transport material. Examples of materials are phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; phosphonic acids and silane derivatives. Self-assembling monomers derived from compounds such as; MoO_xMetal oxide derivatives such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonitrile and other p-type semiconductor organic compounds; including, but not limited to, metal complexes and crosslinkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL have the following general structure:<chemistry num="30"><img file="JP6869293B2_D0032.tif" /></chemistry>Including, but not limited to.

Ar¹From Ar⁹Also selected from the group consisting of 2 to 10 cyclic structural units of the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and directly. Alternatively, they are bonded to each other via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic cyclic group. Here, each Ar is hydrogen, dehydrogen, 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 substituents selected from the group consisting of combinations thereof.

In one aspect, Ar¹From Ar⁹teeth,<chemistry num="31"><img file="JP6869293B2_D0033.tif" /></chemistry>Selected independently from the group consisting of.

k is an integer from 1 to 20; X¹From X⁸Is C (including CH) or N; Ar¹Has the same groups as defined above.

Examples of metal complexes used in HIL or HTL include the following general formula:<chemistry num="32"><img file="JP6869293B2_D0034.tif" /></chemistry>Including, but not limited to.

M is a metal with an atomic weight greater than 40; (Y¹-Y²) Is a bidentate ligand, Y¹And Y²Is independently selected from C, N, O, P and S; L is the co-ligand; m is an integer value from 1 to the maximum number of ligands that can attach to the metal; , M + n is the maximum number of ligands that can adhere to the metal.

In one aspect, (Y¹-Y²) Is a 2-phenylpyridine derivative.

In another embodiment, (Y¹-Y²) Is a carbene ligand.

In another embodiment, M is selected from Ir, Pt, Os and Zn.

In a further embodiment, the metal complex is Fc.⁺For the / Fc couple, it has a minimum oxidation potential of less than about 0.6V in solution. host:

The light emitting layer of the organic EL device in the present invention preferably contains at least a metal complex as a 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 complex or organic compound may be used as long as the triplet energy of the host is larger than that of the dopant. The table below classifies preferred host materials for devices that emit light in each color, but any host material may be used with any dopant as long as the triplet criteria are met.

An example of a metal complex used as a host is the following general formula:<chemistry num="33"><img file="JP6869293B2_D0035.tif" /></chemistry>It is preferable to have.

M is metal; (Y³-Y⁴) Is a bidentate ligand, Y³And Y⁴Is independently selected from C, N, O, P and S; L is the co-ligand; m is an integer value from 1 to the maximum number of ligands that can attach to the metal; , M + n is the maximum number of ligands that can adhere to the metal.

In one embodiment, the metal complex is<chemistry num="34"><img file="JP6869293B2_D0036.tif" /></chemistry>Is.

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

In another embodiment, M is selected from Ir and Pt.

In a further embodiment, (Y³-Y⁴) Is a carbene ligand.

And the same or different types of groups selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and directly or directly or with oxygen, nitrogen, sulfur, silicon, phosphorus atoms. , Boron atoms, chain structural units and selected from the group consisting of 2 to 10 cyclic structural units bonded to each other via at least one of the aliphatic cyclic groups. Here, each group is hydrogen, dehydrogen, 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 substituents selected from the group consisting of combinations thereof.

In one embodiment, the host compound is in the molecule the following group:<chemistry num="35"><img file="JP6869293B2_D0037.tif" /></chemistry>Contains at least one of.

R¹From R⁷Independently, hydrogen, dehydrogen, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, Selected from the group consisting of carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino and combinations thereof, if it is aryl or heteroaryl, the same definition as Ar mentioned above. Has.

k is an integer from 0 to 20.

X¹From X⁸Is selected from C (including CH) or N. Z¹And Z²Is NR¹, O, and S are selected. HBL:

The hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons emanating from the light emitting layer. The presence of such a blocking layer in a device can result in significantly higher efficiency compared to similar devices lacking a blocking layer. A blocking layer can also be used to limit light emission to the desired region of the OLED.

In one aspect, the compound used in the HBL contains the same molecules used as the hosts described above.

In another embodiment, the compounds used in the HBL have the following groups in the molecule:<chemistry num="36"><img file="JP6869293B2_D0038.tif" /></chemistry>Contains at least one of.

k is an integer from 0 to 20; L is a co-ligand and m is an integer from 1 to 3. ETL:

The electron transport layer (ETL) may include materials capable of transporting electrons. The electron transport layer may be genuine (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited and any metal complex or organic compound may be used as long as it is typically used to transport electrons.

In one embodiment, the compounds used in the ETL are in the following groups in the molecule:<chemistry num="37"><img file="JP6869293B2_D0039.tif" /></chemistry>Contains at least one of.

R¹Is hydrogen, dehydrogen, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid. , Esters, nitriles, isonitriles, sulfanyls, sulfinyls, sulfonyls, phosphinos and combinations thereof, where if they are aryl or heteroaryl, they have the same definitions as those of Ar mentioned above.

Ar¹From Ar³Has a definition similar to that of Ar mentioned above.

k is an integer from 0 to 20.

X¹From X⁸Is selected from C (including CH) or N.

In another embodiment, the metal complex used in the ETL has the following general formula:<chemistry num="38"><img file="JP6869293B2_D0040.tif" /></chemistry>Is contained, but is not limited to these.

(ON) or (NN) is a bidentate ligand with a metal coordinated to the atom O, N or N, N; L is a co-ligand; m is attached to the metal from 1 An integer value up to the maximum number of possible ligands.

In any of the compounds mentioned above used in each layer of the OLED device, the hydrogen atom may be partially or completely deuterated. Thus, any specifically listed substituents such as, but not limited to, methyl, phenyl, pyridyl, etc. are not deuterated, partially deuterated, and fully deuterated. Includes hydrogenated version. Similarly, the classes of substituents such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc. are not deuterated, partially deuterated, and fully deuterated. Also includes the version that was made.

In addition to and / or in combination with the materials disclosed herein, many hole injection materials, hole transport materials, host materials, dopant materials, exciton / hole blocking layer materials, electron transport and Electron injection materials can be used in OLEDs. Non-limiting examples of materials that can be used in combination with the materials disclosed herein in OLEDs are listed in Table 3 below. Table 3 lists a non-limiting class of materials, non-limiting examples of compounds for each class, and references that disclose the material.<tables num="3-1"><img file="JP6869293B2_D0041.tif" /></tables><tables num="3-2"><img file="JP6869293B2_D0042.tif" /></tables><tables num="3-3"><img file="JP6869293B2_D0043.tif" /></tables><tables num="3-4"><img file="JP6869293B2_D0044.tif" /></tables><tables num="3-5"><img file="JP6869293B2_D0045.tif" /></tables><tables num="3-6"><img file="JP6869293B2_D0046.tif" /></tables><tables num="3-7"><img file="JP6869293B2_D0047.tif" /></tables><tables num="3-8"><img file="JP6869293B2_D0048.tif" /></tables><tables num="3-9"><img file="JP6869293B2_D0049.tif" /></tables><tables num="3-10"><img file="JP6869293B2_D0050.tif" /></tables><tables num="3-11"><img file="JP6869293B2_D0051.tif" /></tables><tables num="3-12"><img file="JP6869293B2_D0052.tif" /></tables><tables num="3-13"><img file="JP6869293B2_D0053.tif" /></tables><tables num="3-14"><img file="JP6869293B2_D0054.tif" /></tables><tables num="3-15"><img file="JP6869293B2_D0055.tif" /></tables><tables num="3-16"><img file="JP6869293B2_D0056.tif" /></tables><tables num="3-17"><img file="JP6869293B2_D0057.tif" /></tables><tables num="3-18"><img file="JP6869293B2_D0058.tif" /></tables><tables num="3-19"><img file="JP6869293B2_D0059.tif" /></tables><tables num="3-20"><img file="JP6869293B2_D0060.tif" /></tables><tables num="3-21"><img file="JP6869293B2_D0061.tif" /></tables><tables num="3-22"><img file="JP6869293B2_D0062.tif" /></tables>

The chemical abbreviations used herein are as follows: dba is dibenzylideneacetone, EtOAc is ethyl acetate, PPh₃Is triphenylphosphine, dppf is 1,1'-bis (diphenylphosphino) ferrocene, DCM is dichloromethane, SPhos is dicyclohexyl (2', 6'-dimethoxy- [1,1'-biphenyl] -3. -Il) Phosphine, THF is tetrahydrofuran.

Synthetic

Synthesis of compound 17 1<chemistry num="39"><img file="JP6869293B2_D0063.tif" /></chemistry>

4-Iododibenzo [b, d] furan (18.4 g, 62.6 mmol) in DMF (200 mL), 1H-imidazole (5.11 g, 75 mmol), CuI (0.596 g, 3.13 mmol), Cs₂CO₃A mixed solution of (42.8 g, 131 mmol) and cyclohexane-1,2-diamine (1.43 g, 12.51 mmol) was heated under nitrogen at 150 ° C. for 20 hours. After cooling to room temperature, it was quenched with water and extracted with ethyl acetate. The combined extracts were washed with saline and filtered through a short plug of silica gel. The solvent was evaporated and the crude product was dissolved in ethyl acetate and precipitated in hexanes to give 1-dibenzo [b, d] furan-4-yl) -1H-imidazole (12.2 g, 83%). Obtained as a white solid.

Process 2<chemistry num="40"><img file="JP6869293B2_D0064.tif" /></chemistry>

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

Process 3<img file="JP6869293B2_D0065.tif" />

1- (dibenzo [b, d] furan-4-yl) -3-methyl-1H-imidazol-3-urium iodide (2.5 g, 6.65 mmol) and Ag in acetonitrile (150 mL)₂The mixture of O (0.770 g, 3.32 mmol) was stirred under nitrogen overnight. After evaporation of the solvent, iridium phenylimidazole complex (2.58 g, 2.215 mmol) and THF (150 mL) were added. The resulting reaction mixture was refluxed under nitrogen overnight. After cooling to room temperature, the solid was washed with DCM by filtering through a short plug of Celite®. The combined filtrate was evaporated, and the residue was purified by column chromatography using silica gel treated with triethylamine and hexane / DCM (9/1 to 3/1, v / v) as the eluent, and the mer compound 17 (1.9 g, 72%) was obtained as a yellow-green solid.

Process 4<chemistry num="41"><img file="JP6869293B2_D0066.tif" /></chemistry>

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

Compound 1 Synthesis Step 1<img file="JP6869293B2_D0067.tif" />

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

Process 2<chemistry num="42"><img file="JP6869293B2_D0068.tif" /></chemistry>

Salt (1.09 g, 3.8 mmol) obtained in step 1, Ag₂O (0.445 g, 1.9 mmol) and dry acetonitrile (150 mL) were placed in a 250 mL flask. The resulting mixture was stirred at room temperature overnight to evaporate the solvent. Iridium dimer (2.5 g, 1.267 mmol) and 150 mL of THF were added to the residue. The reaction mixture was then refluxed overnight. The mixture was cooled and passed through a Celite® bed with THF. After evaporating THF and washing with methanol, crude mer isomers (2.3 g, 82%) were obtained.

Process 3<chemistry num="43"><img file="JP6869293B2_D0069.tif" /></chemistry>

The mer isomer (2.0 g, 1.803 mmol) obtained in step 2 was dissolved in DMSO (150 mL) while heating in a photoreaction flask. The resulting mixture was cooled to room temperature. In solution, N several times₂Was fed and purged, and then N until HPLC showed that the mer isomer was converted to the fac isomer.₂It was irradiated with a UV lamp underneath for 7 hours. The product was purified by silica gel column chromatography using a hexane solution of DCM as the eluent. After passing through the column, a pure fac complex (1.0 g, 50%) was obtained. Both NMR and LC-MS have been shown to be the desired products.

Synthesis of compound 33

Process 1<chemistry num="44"><img file="JP6869293B2_D0070.tif" /></chemistry>

4-Bromo-2,3-dihydro-1H-indene-1-one (9.5 g, 45.0 mmol) was added slowly to trifluoroacetic acid (TFA) (100 mL) at ice temperature. NaBH₄(8.51 g, 225 mmol) was added in portions. This was stirred in an ice bath for 1 hour and then warmed to room temperature. The reaction mixture was poured into an ice bath and the pH was adjusted to 8 with aqueous NaOH solution. Extract the mixture with DCM and Na₂SO₄It was dried in and filtered. The organic mixture was purified by silica gel column chromatography (100% hexane) to give 4-bromo-2,3-dihydro-1H-indene (4.9 g, 55%).

Process 2<chemistry num="45"><img file="JP6869293B2_D0071.tif" /></chemistry>

4-Bromo-2,3-dihydro-1H-indene (2.5 g, 12.7 mmol), imidazole (1.9 g, 28 mmol), CuI (0.5 g, 2.6 mmol), Cs₂CO₃N a mixture of (8.7 g, 27 mmol), cyclohexane-1,2-diamine (0.29 g, 2.5 mmol) and DMF (50 mL).₂It was purged with and heated at 150 ° C for 2 days. The reaction was cooled and DCM was added. The organic layer is washed with water followed by an aqueous LiCl solution and Na₂SO₄Dry, filter, concentrate, vacuum distill at 190 ° C (Kugelrohr), 1- (2,3-dihydro-1H-inden-4-yl) -1H-imidazole (2.0 g, 86.0%) Obtained.

Process 3<chemistry num="46"><img file="JP6869293B2_D0072.tif" /></chemistry>

Iodomethane (7.5 g, 53 mmol) was added to a solution of 1- (2,3-dihydro-1H-indene-4-yl) -1H-imidazole (2.0 g, 10.5 mmol) in ethyl acetate (40 mL). The reaction was stirred at room temperature overnight. The obtained crystals were filtered and washed with ethyl acetate. As a result, N-methyliodide salt (2.7 g, 79%) was obtained.

Process 4<chemistry num="47"><img file="JP6869293B2_D0073.tif" /></chemistry>

N-methyliodide salt (1.09 g, 3.34 mmol), Ag₂N a mixture of O (0.39 g, 1.67 mmol) and anhydrous acetonitrile (90 mL)₂It was purged with and stirred at room temperature overnight. The reaction was concentrated to remove acetonitrile. Iridium dimer (2.2 g, 1.11 mmol) was added with THF (90 mL) and refluxed overnight. After cooling to room temperature, the mixture was filtered through Celite® and concentrated. The residue was subjected to chromatography (TEA-treated column) eluting with hexane: DCM (1: 1, v / v) to give the mer isomer (2.9 g wet, 113%).<chemistry num="48"><img file="JP6869293B2_D0074.tif" /></chemistry>

N in a solution of mer isomers (2.9 g, 1.9 mmol) in DMSO (250 mL)₂UV light was applied for 9 hours below. DMSO was removed under vacuum at 145 ° C (Kugelrohr) and the residue was subjected to chromatography (TEA-treated column) using hexane: dichloromethane as an eluent, further dissolved in dichloromethane and isopropyl alcohol and concentrated to dichloromethane. Was purified by removing. The resulting crystals were filtered and washed with isopropanol to give pure compound 33 (0.55 g, 19%).

It is understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. Accordingly, the invention as claimed can include variations from the particular examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It is understood that the various theories as to why the present invention works are not intended to be limiting.

<p><patcit num="1"><text>U.S. Pat. No. 5,844,363</text></patcit><patcit num="2"><text>U.S. Pat. No. 6,303,238</text></patcit><patcit num="3"><text>U.S. Pat. No. 5,707,745</text></patcit><patcit num="4"><text>U.S. Pat. No. 7,279,704</text></patcit></p>

100 Organic light emitting device 110 Substrate 115 Anode 120 Hole injection layer 125 Hole transport layer 130 Electron blocking layer 135 Light emitting layer 140 Hole blocking layer 145 Electron transport layer 150 Electron injection layer 155 Protective layer 160 Cathode 162 First conductive layer 164 Second Conductive Layer 170 Barrier Layer 200 Inverted OLED, Device 210 Substrate 215 Cone 220 Emitting Layer 225 Hole Transport Layer 230 Anode