Iridium complexes with methyl-d3 substitution

Abstract

The present invention relates to iridium complexes with methyl-D3 substitution. Provided are new organic compounds that include deuterium substituted ligands. In particular, the compounds are iridium complexes that include methyl-d3 substituted ligands. The compounds can be used in organic light emitting devices to provide devices with improved color, efficiency, and lifetime.

Description

[0001] This patent application is a divisional application of Chinese Patent Application No. 201510482186.3, which has a priority date of April 28, 2009 and is entitled "Iridium Complexes with Methyl-D3 Substitution".

[0002] This application claims priority to U.S. Provisional Application No. 61 / 173,346, filed April 28, 2009, and U.S. Application No. 12 / 768,068, filed April 27, 2010, the disclosures of which are expressly incorporated herein by reference in their entirety.

[0003] The claimed invention was made, on behalf of, and / or in connection with one or more of the following parties to the joint university-corporation research agreement: the University of Michigan Board of Trustees, Princeton University, the University of Southern California, and General Display Corporation. This agreement was in effect on and prior to the date of the claimable invention, and the claimable invention was made as a result of activities carried out within the scope of this agreement. Technical Field

[0004] This invention relates to novel organic compounds that can be advantageously used in organic light-emitting devices. More particularly, this invention relates to novel methyl-d3-substituted iridium complexes and their use in OLEDs. Background Technology

[0005] Optoelectronic devices utilizing organic materials are becoming increasingly popular for many reasons. Many of the materials used to fabricate such devices are relatively inexpensive, giving organic optoelectronic devices a potential cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them well-suited for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can exhibit superior performance compared to conventional materials. For instance, the wavelength emitted by an organic light-emitting layer can often be easily tuned using suitable dopants.

[0006] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly advantageous technology in applications such as flat panel displays, lighting, and backlighting. Various OLED materials and structures are described in U.S. Patent Nos. 5,844,363, 6,303,238, and 5,707,745, all of which are incorporated herein by reference.

[0007] One application of phosphorescent molecules is in full-color displays. Industry standards for such displays require pixels suitable for emitting specific colors known as "saturated" colors. Specifically, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates, which are well-known in the art.

[0008] An example of a green-emitting molecule is tris(2-phenylpyridine)iridium, denoted as Ir(ppy)3, which has the structure of formula I:

[0009]

[0010] In this figure and the following figures, we represent the coordination bond from nitrogen to the metal (Ir in this case) as a straight line.

[0011] As used in this article, the term "organic" includes both polymeric materials and small-molecule organic materials that can be used to prepare organic optoelectronic devices. "Small molecule" refers to any non-polymeric organic material, and "small molecule" can actually be quite large. In some cases, small molecules can contain repeating units. For example, using a long-chain alkyl group as a substituent does not exclude the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups of the polymer backbone or as part of the backbone. Small molecules can also serve as the core structural part of dendritic compounds, which consist of a series of chemical shells built on top of the core structural part. The core structural part of a dendritic compound can be a fluorescent or phosphorescent small-molecule luminescent material. Dendritic compounds can be "small molecules," and it is believed that all dendritic compounds currently used in the OLED field are small molecules.

[0012] In this article, "top" refers to the furthest point from the substrate, while "bottom" refers to the closest point to the substrate. When the first layer is described as "on top of the second layer," the first layer is further away from the substrate. Other layers may exist between the first and second layers unless explicitly stated that the first and second layers are in "contact." For example, the cathode may be described as "on top of the anode," even if multiple organic layers exist in between.

[0013] As used in this article, "solvable" means capable of being dissolved, dispersed or transported in a liquid medium and / or deposited from a liquid medium in the form of a solution or suspension.

[0014] When a ligand is considered to directly contribute to the photoactive properties of a luminescent material, it can be called "photoactive." When a ligand is considered not to contribute to the photoactive properties of a luminescent material, it can be called "auxiliary," even though auxiliary ligands can alter the properties of photoactive ligands.

[0015] As used herein, and as commonly understood by those skilled in the art, a first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” (LUMO) level is “greater than” or “higher than” a second HOMO or LUMO level if the first level is closer to the vacuum level. Since ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to a smaller absolute value of IP (lower negative IP). Similarly, a higher LUMO level corresponds to a smaller absolute value of electron affinity (EA) (lower negative EA). On a conventional energy level diagram, the vacuum level is at the top, and the LUMO levels of a material are higher than the HOMO levels of the same material. “Higher” HOMO or LUMO levels appear closer to the top of the diagram compared to “lower” HOMO or LUMO levels.

[0016] As used herein, and as commonly understood by those 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 the work function is typically measured as a negative number relative to the vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, the vacuum level is at the top, and a “higher” work function is represented by a work function that is further away from the vacuum level in a downward direction. Therefore, the definitions of HOMO and LUMO levels follow a different convention than those for the work function.

[0017] For further details regarding OLEDs and the above definition, see U.S. Patent No. 7,279,704, the entire disclosure of which is incorporated herein by reference. Summary of the Invention

[0018] Compounds containing ligands having the following structures:

[0019] A and B can independently represent a 5- or 6-membered aromatic ring or a heteroaromatic ring. Preferably, A is selected from imidazole, pyrazole, triazole, oxazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine. Preferably, B is selected from benzene, pyridine, furan, pyrrole, and thiophene. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X B Independently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A RB At least one of R1 and R2 includes CD3. A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with a metal having an atomic weight greater than 40. Preferably, the metal is Ir.

[0020] On the one hand, the ligand has the following structure:

[0021]

[0022] On the one hand, X A and X B Independently C or N, and when X A When the value is N, R1 is aryl. On the other hand, X A and X B Independently C or N, and when X A When N is present, R1 is a phenyl group, which is further substituted by a group selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups, and wherein the group includes at least one of CD, CD2 or CD3.

[0023] On the one hand, compounds are provided in which the substituent R is located. A and R B At least one of them is CD3, which is directly attached to ring A, ring B, or a ring conjugate or fused with ring A or ring B.

[0024] In particular, compounds comprising a ligand are provided, wherein the ligand is selected from:

[0025]

[0026] R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3.

[0027] On the other hand, the compound contains ligands selected from formulas II, III, IV, V, VI, and VII. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them includes CD3.

[0028] On the other hand, compounds containing ligands are provided, the ligands being selected from:

[0029]

[0030] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be connected. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be fused. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 At least one of them includes an alkyl group, which includes CD, CD2 or CD3.

[0031] Specific examples of methyl-deuterium substituted (also referred to herein as methyl-d3 or CD3) iridium complexes are provided, including compounds selected from compounds 2-42. On one hand, compounds are provided that contain ligands having formula II, such as compounds 2-4. On the other hand, compounds are provided that contain ligands having formula III, such as compounds 5-9. Furthermore, compounds are provided that contain ligands having formula IV, such as compounds 10-14 and 27-40. Further, compounds are provided that contain ligands having formula V, such as compounds 15-19. Still further, compounds are provided that contain ligands having formula VI, such as compounds 20-23. And further, compounds are provided that contain ligands having formula VII, such as compounds 24-26, 41, and 42.

[0032] Further specific examples of deuterium-substituted compounds include compounds selected from compounds 43-82. On one hand, compounds are provided that contain ligands having formula III, such as compounds 58, 59, 68-70, and 75-77. On the other hand, compounds are provided that contain ligands having formula IV, such as compounds 43-52, 62-67, and 80-82. Furthermore, compounds are provided that contain ligands having formula V, such as compounds 55-57, 73, and 74. Further, compounds are provided that contain ligands having formula VI, such as compounds 60, 61, 78, and 79. Further, compounds are provided that contain ligands having formula VIII, such as compounds 53, 54, 71, and 72.

[0033] On the one hand, homooleptic compounds are provided. In particular, compounds are provided in which the ligand having formula I is a ligand in a homooleptic compound. On the other hand, heterooleptic compounds are provided. In particular, compounds are provided in which the ligand having formula I is a ligand in a heterooleptic compound.

[0034] An organic light-emitting device is also provided. This device may include an anode, a cathode, and an organic light-emitting layer located between the anode and the cathode. The organic layer further includes a ligand having a structure of Formula I, as described above.

[0035] A and B can independently represent 5- or 6-membered aromatic rings or heteroaromatic rings. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X B Independently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A R B At least one of R1 and R2 includes CD3. A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with metals having an atomic weight greater than 40.

[0036] On the one hand, XA and X B Independently C or N, and when X A When the value is N, R1 is aryl. On the other hand, X A and X B Independently C or N, and when X A When N is present, R1 is a phenyl group, which is further substituted by a group selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups, and wherein the group includes at least one of CD, CD2 or CD3.

[0037] The preferred choice of aromatic ring, metal, and substituent for compounds containing I-type ligands is also preferred for devices comprising compounds containing I-type ligands. These choices include metal M, rings A and B, and substituent R. A R B Those mentioned in A1, A2, B1, B2, R1, and R2.

[0038] Preferably, the substituent R A and R B At least one of them is CD3, which is directly attached to ring A, ring B, or a ring conjugate or fused with ring A or ring B.

[0039] Preferably, the metal is Ir.

[0040] Preferably, A is selected from imidazole, pyrazole, triazole, oxazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine. Preferably, B is selected from benzene, pyridine, furan, pyrrole, and thiophene.

[0041] In particular, the organic layer of the device may comprise compounds having ligands selected from formulas II-VII, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3. Preferably, the organic layer comprises a compound selected from compounds 2-42.

[0042] Furthermore, the organic layer of the device may comprise compounds having ligands selected from formulas II-VII, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3.

[0043] Furthermore, the organic layer of this device may contain compounds having ligands selected from formulas III-VIII. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be connected. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be fused. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 At least one of the compounds comprises an alkyl group, including CD, CD2, or CD3. Preferably, the organic layer comprises a compound selected from compounds 43-82.

[0044] On one hand, the organic layer is a light-emitting layer containing a compound provided herein, wherein the compound is a light-emitting dopant. The organic layer may further comprise a host. Preferably, the host has the following formula:

[0045] R'1, R'2, R'3, R'4, R'5, and R'6 may represent monosubstituted, disubstituted, trisubstituted, or tetrasubstituted substances; and each of R'1, R'2, R'3, R'4, R'5, and R'6 is independently selected from hydrogen, alkyl, and aryl. More preferably, the main body is H1.

[0046] Consumer products incorporating the device are also provided. The device includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer contains compounds containing ligands of formula I, as discussed above.

[0047] A and B can independently represent 5- or 6-membered aromatic rings or heteroaromatic rings. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X B Independently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A R B At least one of R1 and R2 includes CD3.A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with metals having an atomic weight greater than 40.

[0048] The preferred choice of aromatic ring, metal, and substituent for compounds containing the I-ligand is also preferred for use in consumer products comprising devices that include compounds containing the I-ligand. These choices include metal M, rings A and B, and substituent R. A R B Those mentioned in A1, A2, B1, B2, R1, and R2. Attached Figure Description

[0049] Figure 1 An organic light-emitting device is shown.

[0050] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is shown.

[0051] Figure 3 The general structure of the ligand containing deuterium substitution is shown.

[0052] Figure 4 An exemplary methyl-d3 substituted ligand is shown. Detailed Implementation

[0053] Typically, an OLED comprises at least one organic layer located between and electrically connected to both an anode and a cathode. When a current is applied, the anode injects holes into the organic layer, and the cathode injects electrons into the organic layer. The injected holes and electrons migrate toward electrodes with opposite charges. When electrons and holes are confined within the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a luminescence mechanism, light is emitted. In some cases, excitons can be localized on an exciter or an exciter complex. Non-radiative mechanisms, such as thermal relaxation, can also occur, but these are generally considered undesirable.

[0054] Early OLEDs used luminescent molecules that emitted light from their singlet states (“fluorescence”), as disclosed in, for example, U.S. Patent No. 4,769,292, the entire contents of which are incorporated herein by reference. Fluorescence emission typically occurs in a timeframe of less than 10 nanoseconds.

[0055] Recently, OLEDs with luminescent materials exhibiting emission from the triplet state (“phosphorescence”) have been demonstrated. See 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”), both of which are incorporated herein by reference. Phosphorescence is described in more detail in columns 5-6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0056] Figure 1 Organic light-emitting device 100 is shown. These figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, a light-emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and a cathode 160. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the above layers sequentially. The properties and functions of these different layers, as well as examples of materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0057] Further examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, the entire contents of which are incorporated herein by reference. An example of a p-type doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, disclosed in U.S. Patent Application Publication No. 2003 / 0230980, the entire contents of which are incorporated herein by reference. Examples of luminescent materials and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., the entire contents of which are incorporated herein by reference. An example of an n-type doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, disclosed in U.S. Patent Application Publication No. 2003 / 0230980, the entire contents of which are incorporated herein by reference. U.S. Patent Nos. 5,703,436 and 5,707,745 (the entire contents of which are incorporated herein by reference) disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg:Ag with a covering transparent conductive sputter-deposited ITO layer. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, the entire contents of which are incorporated herein by reference. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, the entire contents of which are incorporated herein by reference. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, the entire contents of which are incorporated herein by reference.

[0058] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, a light-emitting layer 220, a hole transport layer 225, and an anode 230. Device 200 can be fabricated by sequentially depositing the layers. Because most conventional OLED structures have a cathode located above the anode, while device 200 has a cathode 215 located below the anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described for device 100 can be used in the corresponding layers of device 200. Figure 2 Examples are provided of how certain layers can be omitted from the structure of device 100.

[0059] Figure 1 and 2The simple layered structure shown is provided by way of non-limiting example, and it should be understood that embodiments of the invention can be used in combination with many other structures. The specific materials and structures described are exemplary, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described above in different ways or by omitting layers entirely, depending on design, performance, and cost factors. Other layers not explicitly stated may also be included. Materials other than those explicitly stated can be used. Although many examples provided herein describe multiple layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of a host and dopant or more generally, mixtures can be used. Additionally, layers can have multiple sublayers. The names given to various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into light-emitting layer 220, and can 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 anode. This organic layer can comprise a single layer, or can further comprise, as for… Figure 1 and 2 Multiple layers of different organic materials as described in the text.

[0060] Structures and materials not explicitly described may also be used, such as OLEDs (PLEDs) including polymer materials, as disclosed in U.S. Patent No. 5,247,190 to Friend et al., the entire contents of which are incorporated herein by reference. As a further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, as described, for example, in U.S. Patent No. 5,707,745 to Forrest et al., the entire contents of which are incorporated herein by reference. OLED structures may deviate from... Figure 1 and 2 The simple layered structure shown is illustrated. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to Forrest et al. and / or the pit structure described in U.S. Patent No. 5,834,893 to Bulovic et al., the entire contents of which are incorporated herein by reference.

[0061] Unless otherwise stated, any layer in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing, such as those described in U.S. Patent Nos. 6,013,982 and 6,087,196, the entire contents of which are incorporated herein by reference; organic vapor deposition (OVPD), such as those described in U.S. Patent No. 6,337,102 to Forrest et al., the entire contents of which are incorporated herein by reference; and deposition by organic vapor phase spraying (OVJP), such as those described in U.S. Patent Application No. 10 / 233,470, the entire contents of which are incorporated herein by reference. Other suitable deposition methods include spin coating and other solution-based methods. Solution-based methods are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include mask deposition, cold soldering, as described in, for example, U.S. Patent Nos. 6,294,398 and 6,468,819, the entire contents of which are incorporated herein by reference; and patterning methods associated with certain deposition methods such as inkjet printing and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a specific deposition method. For example, substituents, such as branched or unbranched alkyl and aryl groups, preferably containing at least 3 carbons, may be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. Materials with asymmetric structures may have better solution handling ability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic substituents may be used to improve the solution handling ability of small molecules.

[0062] Devices prepared according to embodiments of the present invention can be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, televisions, billboards, indoor or outdoor lighting and / or signal lights, hazard warning displays, fully transparent displays, flexible displays, laser printers, telephones, mobile phones, personal digital assistants (PDAs), laptops, digital cameras, portable video cameras, viewfinders, miniature displays, vehicles, large-area walls, theater or stadium screens or signs. Various control mechanisms can be used to control the devices prepared according to the present invention, including passive and active matrices. Many devices are intended for use within a temperature range comfortable for the human body, such as 18°C ​​to 30°C, more preferably room temperature (20 to 25°C).

[0063] The materials and structures described herein can be applied to devices other than OLEDs. For example, these materials and structures can be used in other optoelectronic devices such as organic solar cells and organic photodetectors. More generally, these materials and structures can be used in organic devices such as organic transistors.

[0064] The terms halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group and heteroaryl are known in the art and are defined in columns 31-32 of US 7,279,704, which is incorporated herein by reference.

[0065] As used herein, the terms alkyl, aryl, and heteroaryl also include deuterium in place of hydrogen. For example, alkyl can include CH3 or CD3, as well as CH2CH3 or CH2CD3. Similarly, aryl and heteroaryl can include aromatic groups substituted with deuterium instead of hydrogen.

[0066] The substitution of hydrogen with its isotope deuterium in iridium complexes has been reported in the literature (see, for example, U.S. Patent Publication No. 2008 / 0194853 and U.S. Patent No. 6,699,599). In particular, direct deuterium substitution on the ring does not appear to provide color modulation. Specifically, the inventors are unaware of any reports regarding changes in the luminescent properties of compounds substituted with deuterium atoms.

[0067] CD3 substitution in the host material has also been reported (see WO2008029670). However, the luminescence properties of the luminescent dopant are an important property of the compound, and substitution of the host material does not provide any information about color modulation. In particular, when the modified compound is the host material rather than the luminescent material (as presented herein), the effect of deuterium substitution on the photoluminescence spectrum (e.g., color modulation properties) cannot be evaluated. Therefore, luminescent compounds with improved stability associated with deuterium and the advantageous properties of methyl substitution (i.e., color modulation, improved quantum efficiency, and improved lifetime) may be desirable.

[0068] Methyl substitution in metal complexes has been shown to be useful for modulating the photophysical and electroluminescent properties of the compounds. For example, methyl substitution at certain positions can be beneficial to their stability, thereby improving quantum efficiency, spectral shape, and OLED lifetime.

[0069] This article presents a novel compound comprising a ligand having a methyl-d3 substituent (shown in...). Figure 3 (in Chinese). In addition, specific ligands containing methyl-d3 substitution are provided (shown in...). Figure 4 (in Chinese). In particular, the use of publicly available compounds can provide both improved photoluminescence and improved device efficiency.

[0070] The compounds presented herein contain ligands with methyl-d3 substitution. These compounds can be advantageously used in OLEDs to provide devices with improved efficiency, long lifetime, and improved color (e.g., color tuning). Without being theoretically limited, it is believed that CD3 substituents can improve stability due to strong CD bonds. As discussed above, the strength of CD bonds is greater than that of CH bonds. Furthermore, the smaller van der Waals radius of deuterium can be translated into smaller substituent volumes (e.g., smaller torsion on the aromatic ring containing a CD3 substituent at the ortho position instead of a CH3 substituent) and thus improved conjugation in systems with CD3 substitution. Moreover, the reaction rate of chemical processes involving CD bonds present in the methyl-d3 can be slower due to kinetic isotope effects. If the chemical degradation of the luminescent compound involves breaking the methyl-CH bond, then stronger CD bonds can improve the stability of the compound.

[0071] Methyl groups are the simplest alkyl substituents added to compounds as modifications. They can be very important substituents to alter the properties of both the host and emitter in OLEDs. Methyl groups can affect solid-state stacking properties (i.e., sublimation and charge transport properties), change photophysical properties, and influence device stability. Methyl substituents have been introduced to modify the properties of tris(2-phenylpyridine)iridium(III) ions. For example, devices with tris(3-methyl-2-phenylpyridine)iridium(III) as emitters exhibit better stability than those with tris(2-phenylpyridine)iridium(III) as emitters. Furthermore, the emission peak of tris(3-methyl-2-phenylpyridine)iridium(III) exhibits a redshift of approximately 10 nm. The evaporation temperature of tris(3-methyl-2-phenylpyridine)iridium(III) is also approximately 20 degrees lower than that of tris(2-phenylpyridine)iridium(III).

[0072] On the other hand, the methyl group is also considered reactive due to the benzyl group. Not limited by theory, the hydrogen atoms present in the methyl group can be particularly active and thus serve as sites for chemical degradation in luminescent compounds. Furthermore, it is widely accepted in the art that dopant compounds are oxidized during OLED operation. In the oxidized state, the benzyl position can become the weakest position, leading to further chemical degradation. The proposed mechanism may be more relevant when the luminescent dopant is used with certain hosts such as triphenylene / DBT hybrid materials, and less relevant with other hosts such as Balq. Therefore, replacing the hydrogen atoms in the methyl group with deuterium atoms (methyl-d3) can stabilize the luminescent compound.

[0073] It is believed that deuterium substitution can improve efficiency and stability because deuterium has twice the atomic mass of hydrogen, resulting in a lower zero-point energy and lower vibrational energy levels. Furthermore, the bond lengths and bond angles involved in deuterium differ from those involved in hydrogen. In particular, the van der Waals radius of deuterium is smaller than that of hydrogen due to the smaller stretching of the CD bond compared to the CH bond. Generally, CD bonds are shorter and stronger than CH bonds. Therefore, CD3 substitution can provide the same color tuning as well as all the benefits associated with increased bond strength (i.e., improved efficiency and lifetime).

[0074] As discussed above, deuterium substitution offers numerous benefits, such as improved efficiency and lifetime. Therefore, compounds containing deuterated ligands can be advantageously used in organic light-emitting devices. Such compounds include, for example, compounds containing ligands that have deuterium in the alkyl chain, such as C(D)(H)CH3, CD2CH3, and CH2CD2CH3, and deuterium at the end of the alkyl chain, such as CD3.

[0075] This article presents a novel compound comprising a ligand having the following structure:

[0076] A and B can independently represent a 5- or 6-membered aromatic ring or a heteroaromatic ring. Preferably, A is selected from imidazole, pyrazole, triazole, oxazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine. Preferably, B is selected from benzene, pyridine, furan, pyrrole, and thiophene. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X B Independently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A R B At least one of R1 and R2 includes CD3. A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with a metal having an atomic weight greater than 40. Preferably, the metal is Ir.

[0077] On the one hand, the ligand has the following structure:

[0078]

[0079] On the one hand, X A and X B Independently C or N, and when X A When the value is N, R1 is aryl. On the other hand, X A and X B Independently C or N, and when X A When N is present, R1 is a phenyl group, which is further substituted by a group selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups, and wherein the group includes at least one of CD, CD2 or CD3.

[0080] On the one hand, compounds are provided in which the substituent R is located. A and R B At least one of them is CD3, which is directly attached to ring A, ring B, or a ring conjugate or fused with ring A or ring B.

[0081] As discussed above, the substituent R A and R B It can fuse to ring A and / or ring B. Substituent R A and R B It can be any substituent, including substituents that are attached to, fused to, or not fused to ring A and / or ring B.

[0082] In particular, compounds comprising a ligand are provided, wherein the ligand is selected from:

[0083]

[0084] R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl; and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3.

[0085] In addition, compounds comprising a ligand are provided, wherein the ligand is selected from:

[0086]

[0087] R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl, and R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3.

[0088] Compounds containing ligands, wherein the ligands are selected from:

[0089]

[0090] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl; and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be connected. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be fused. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 At least one of them includes an alkyl group, which includes CD, CD2 or CD3.

[0091] Specific examples of methyl-d3 substituted iridium complexes are provided, including compounds selected from the following:

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] Further specific examples of deuterium-substituted iridium complexes are provided, including compounds selected from the following:

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] On the one hand, compounds are provided, wherein the compounds contain ligands of formula II, such as compounds 2-4.

[0105] On the other hand, compounds are provided that contain ligands of formula III, such as compounds 5-9.

[0106] On the other hand, other compounds containing the formula III ligand are provided, including compounds 58, 59, 68-70 and 75-77.

[0107] On the other hand, compounds are provided that contain ligands of formula IV, such as compounds 10-14 and 27-40.

[0108] On the other hand, other compounds containing IV ligands are provided, including compounds 43-52, 62-67 and 80-82.

[0109] On the other hand, compounds are provided, wherein the compounds contain ligands of formula V, such as compounds 15-19.

[0110] On the other hand, other compounds containing V ligands are provided, including compounds 55-57, 73 and 74.

[0111] On the other hand, compounds are provided, wherein the compounds contain ligands of formula VI, such as compounds 20-23.

[0112] On the other hand, other compounds containing VI ligands are provided, including compounds 60, 61, 78 and 79.

[0113] On the other hand, compounds are provided that contain ligands of formula VII, such as compounds 24-26, 41 and 42.

[0114] On the other hand, compounds containing formula III ligands are provided, including compounds 53, 54, 71 and 72.

[0115] Compounds containing ligands selected from formulas II, III, IV, V, VI, and VII can be particularly stable dopant compounds.

[0116] Furthermore, compounds containing ligands of formula VIII can also be particularly stable compounds.

[0117] On the one hand, homocoordination compounds containing CD3 are provided. In particular, compounds are provided in which the ligand of formula I is a ligand in a homocoordination compound. The homocoordination compounds provided herein include, for example, compounds 2-19. On the other hand, heterocoordination compounds containing CD3 are provided. In particular, compounds are provided in which the ligand of formula I is a ligand in a heterocoordination compound. The heterocoordination compounds provided herein include, for example, compounds 20-42. Heterocoordination compounds containing CD3 can include compounds having luminescent and non-luminescent ligands, such as compounds 20-26, which contain two luminescent ligands and one acac ligand. Furthermore, heterocoordination compounds containing CD3 can include compounds in which all ligands are luminescent ligands and these luminescent ligands have different structures. On the one hand, heterocoordination compounds containing CD3 can have two luminescent ligands containing CD3 and one luminescent ligand without CD3. For example, compounds 27, 33, 35-40. On the other hand, heterocoordination compounds containing CD3 can have one CD3-containing luminescent ligand and two CD3-free luminescent ligands. Examples include compounds 29-32, 41, and 42. The CD3-containing luminescent ligand can contain a single CD3 group (e.g., compounds 29-32), or the ligand can contain multiple CD3 groups (e.g., compounds 41 and 42 contain a luminescent ligand with two CD3 substituents). Furthermore, heterocoordination compounds containing CD3 can contain two or more luminescent ligands of different types, where all ligands contain CD3. Examples include compounds 28 and 34.

[0118] Furthermore, an organic light-emitting device is provided. The device includes an anode, a cathode, and an organic light-emitting layer located between the anode and the cathode. The organic layer comprises a compound containing ligands with the structure described above:

[0119] The preferred choice of aromatic ring, metal, and substituent for compounds containing I-type ligands is also preferred for devices comprising compounds containing I-type ligands. These choices include metal M, rings A and B, and substituent R. A R B Those mentioned in A1, A2, B1, B2, R1, and R2.

[0120] A and B can independently represent a 5- or 6-membered aromatic ring or a heteroaromatic ring. Preferably, A is selected from imidazole, pyrazole, triazole, oxazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine. Preferably, B is selected from benzene, pyridine, furan, pyrrole, and thiophene. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X BIndependently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A R B At least one of R1 and R2 includes CD3. A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with a metal having an atomic weight greater than 40. Preferably, the metal is Ir.

[0121] On the one hand, the ligand has the following structure:

[0122]

[0123] On the one hand, X A and X B Independently C or N, and when X A When the value is N, R1 is aryl. On the other hand, X A and X B Independently C or N, and when X A When N is present, R1 is a phenyl group, which is further substituted by a group selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups, and wherein the group includes at least one of CD, CD2 or CD3.

[0124] On the one hand, compounds are provided in which the substituent R is located. A and R B At least one of them is CD3, which is directly attached to ring A, ring B, or a ring conjugate or fused with ring A or ring B.

[0125] As discussed above, the substituent R A and R B It can fuse to ring A and / or ring B. Substituent R A and R B It can be any substituent, including substituents that are attached to, fused to, or not fused to ring A and / or ring B.

[0126] In particular, the organic layer of the device comprises compounds having ligands selected from formulas II-VII. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them is CD3. Preferably, the organic layer comprises a compound selected from compounds 2-42.

[0127] Furthermore, the organic layer of the device comprises compounds having ligands selected from formulas II-VII. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 At least one of them includes CD3.

[0128] Furthermore, the organic layer of this device may contain compounds having ligands selected from formulas III-VIII. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 Independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be connected. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 They can be fused. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 and R 11 At least one of the compounds comprises an alkyl group, including CD, CD2, or CD3. Preferably, the organic layer comprises a compound selected from compounds 43-82.

[0129] On one hand, the organic layer is a light-emitting layer containing a compound having the provided formula I ligand, wherein the compound is a light-emitting dopant. The organic layer may further comprise a host. Preferably, the host has the following formula:

[0130] R'1, R'2, R'3, R'4, R'5, and R'6 may represent monosubstituted, disubstituted, trisubstituted, or tetrasubstituted substances; and each of R'1, R'2, R'3, R'4, R'5, and R'6 is independently selected from hydrogen, alkyl, and aryl. More preferably, the main body is H1.

[0131] Consumer products incorporating the device are also provided. The device comprises an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer comprises a compound containing ligands with the structure described above:

[0132] The preferred choice of aromatic ring, metal, and substituent for compounds containing I-type ligands is also preferred for devices comprising compounds containing I-type ligands. These choices include metal M, rings A and B, and substituent R. A R B Those mentioned in A1, A2, B1, B2, R1, and R2.

[0133] A and B can independently represent a 5- or 6-membered aromatic ring or a heteroaromatic ring. Preferably, A is selected from imidazole, pyrazole, triazole, oxazole, oxadiazole, pyridine, pyridazine, pyrimidine, pyrazine, and triazine. Preferably, B is selected from benzene, pyridine, furan, pyrrole, and thiophene. A1, A2, B1, and B2 are independently C or N. R A and R B It can represent monosubstituted, disubstituted, or trisubstituted substitution. X A and X B Independently, it can be either a carbon atom or a heteroatom. R A R B R1 and R2 are independently selected from hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl, and heteroaryl. A R B At least one of R1 and R2 includes CD, CD2, or CD3. Preferably, R A R B At least one of R1 and R2 includes CD3. A R B R1 and R2 can be connected. A R B R1 and R2 can fused. This ligand coordinates with a metal having an atomic weight greater than 40. Preferably, the metal is Ir.

[0134] On the one hand, X A and X B Independently C or N, and when X A When the value is N, R1 is aryl. On the other hand, X A and X B Independently C or N, and when X A When N is present, R1 is a phenyl group, which is further substituted by a group selected from alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups, and wherein the group includes at least one of CD, CD2 or CD3.

[0135] The consumer product may include a device that further includes an organic layer containing a compound comprising ligands selected from structures of formulas II-VII. In particular, the compound may be selected from compounds 2-42.

[0136] Furthermore, the organic layer of the device may comprise compounds having ligands selected from formulas III-VIII. Preferably, the organic layer comprises compounds selected from compounds 43-82.

[0137] On the one hand, specific consumer products incorporating the device are provided. Preferably, the device contains a compound wherein the substituent R... A and R B At least one of them is CD3, which is directly attached to ring A, ring B, or a ring conjugate or fused with ring A or ring B.

[0138] As discussed above, the substituent R A and R B It can fuse to ring A and / or ring B. Substituent R A and R B It can be any substituent, including substituents that are attached to, fused to, or not fused to ring A and / or ring B.

[0139] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the light-emitting dopants disclosed herein can be used in combination with various host layers, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or described below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0140] In addition to the materials disclosed herein, and / or in combination with the materials disclosed herein, a wide variety of 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 OLEDs in combination with the materials disclosed herein are listed in Table 1 below. Table 1 lists the non-limiting material categories, non-limiting examples of compounds in each category, and the literature disclosing these materials.

[0141] Table 1

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] experiment

[0155] Compound Examples

[0156] Example 1: Synthesis of Compound 10

[0157]

[0158] Synthesis of 2-bromo-6-phenylpyridine. In a 1L round-bottom flask with a condenser, nitrogen inlet, and two stoppers, 2,6-dibromopyridine (15.3 g, 64.58 mmol), phenylboronic acid (7.87 g, 64.58 mmol), and potassium carbonate (17.85 g, 129.16 mmol) were added to 228 mL of dimethoxyethane and 150 mL of water. Nitrogen was bubbled directly into the mixture for 15 minutes. Tetra(triphenylphosphine)palladium(O) (1.85 g, 1.60 mmol) was added, and the reaction mixture was heated to reflux. The reaction was completed after 3 hours of heating. The mixture was cooled to room temperature and diluted with water and ethyl acetate. The layers were separated, and the aqueous layer was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and evaporated. The product was purified by column chromatography using 2% ethyl acetate / hexane followed by vacuum distillation in a Kugelrohr tube, and collected at 150 °C. 5.2g of product (34%) was obtained.

[0159]

[0160] Synthesis of 2-phenyl-6-methyl-d3-phenylpyridine. A 3-necked 500 mL round-bottom flask fitted with a dropping funnel, nitrogen inlet, and stopper was dried under vacuum using a hot air blower. 2-Bromo-6-phenylpyridine (11.3 g, 48.27 mmol) and 100 mL of dry THF were added to the cooled, dried flask. The solution was cooled under nitrogen in a dry ice / acetone bath, and iodomethane-d3 (6 mL, 96.54 mmol) was added dropwise. The solution was cold-stirred for 1 hour, then warmed to room temperature overnight. It was diluted with water and extracted twice with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered, and evaporated. The crude material was purified twice by column chromatography using 2% ethyl acetate / hexane as elution. 5.8 g of 2-phenyl-6-methyl-d3-pyridine (70%) was obtained.

[0161]

[0162] Synthesis of the dimer. A mixture of 2-phenyl-6-methyl(d3)pyridine (1.65 g, 9.58 mmol), iridium chloride (1.6 g, 4.35 mmol), and 30 mL of 2-ethoxyethanol was heated under nitrogen and refluxed overnight. The mixture was cooled to room temperature and filtered to obtain a red solid. The solid was washed with methanol and hexane and air-dried in a fume hood. 1.09 g of the dimer product (44%) was obtained and used directly in the next step.

[0163]

[0164] Synthesis of the trifluoromethanesulfonate intermediate. A mixture of dimer (1.09 g, 0.956 mmol) and 125 mL of dichloromethane was prepared in a 250 mL round-bottom flask. Silver trifluoromethanesulfonate (0.51 g, 2.00 mmol) in 10 mL of methanol was added to this red mixture, which turned green. The contents of the flask were stirred overnight at room temperature under nitrogen. The mixture was filtered through a Celite pad, and the Celite was rinsed with dichloromethane. The filtrate was evaporated to give a yellow-green solid. The solid was dried under high vacuum. 1 g of solid (71%) was obtained and used directly in the next reaction.

[0165]

[0166] Synthesis of Compound 10. A trifluoromethanesulfonate complex (1 g, 1.3 mmol) and 2-phenyl-6-methyl(d3)pyridine (0.7 g, 4.0 mmol) were added to a 10 mL glass tube, which was then purged with nitrogen. This process was repeated, and the tube was subsequently heated to 200 °C under nitrogen overnight. The tube was cooled and dichloromethane was added to dissolve the material, which was then transferred to a flask. The crude material was purified by column chromatography followed by sublimation at 250 °C using 20, 40, and 50% dichloromethane / hexane elution. 0.58 g of product (63%) was obtained after sublimation.

[0167] Example 2 Synthesis of Compound 13

[0168]

[0169] Synthesis of 3-methyl-d3-2-phenylpyridine. 3-Bromo-2-phenylpyridine (9.9 g, 42 mmol) was dissolved in 100 mL of tetrahydrofuran and cooled to -78 °C. BuLi (26.4 mL, 1.6 M in hexane) was added dropwise to the solution. After the addition was complete, the reaction mixture was stirred at -78 °C for 1 h. Iodomethane-d3 (9.3 g, 63 mmol) was added and the mixture was heated to room temperature for 2 h. The reaction was then abruptly stopped with water and extracted with ethyl acetate. The crude product was purified by column chromatography using hexane and ethyl acetate as eluents. 2.3 g of pure product was obtained after purification.

[0170]

[0171] Synthesis of Compound 13. 3-Methyl-d3-2-phenylpyridine (1.8 g, 10.4 mmol) and Ir(acac)3 (0.64 g, 1.3 mmol) were heated to 260 °C under nitrogen for 48 hours. After cooling to room temperature, dichloromethane was added to dissolve the product. The dichloromethane solution was then poured into hexane. The precipitate was collected and passed through a short silica gel column. 0.6 g of product was obtained. The product was further purified by recrystallization from 1,2-dichlorobenzene.

[0172] Example 3 Synthesis of Compound 27

[0173]

[0174] Synthesis of Compound 27. A trifluoromethanesulfonate complex (1.4 g), 4-methyl-2,5-diphenylpyridine (1.5 g), and 50 mL of ethanol were mixed and refluxed overnight under nitrogen. The precipitate was filtered off. The crude product was purified by column chromatography using 50% dichloromethane / hexane elution. 1.1 g of the target product was obtained.

[0175] Example 4 Synthesis of Compound 43

[0176]

[0177] Synthesis of Compound 43. Iridium trifluoromethanesulfonate complex (1.0 g, 1.3 mmol) and 2-biphenyl-4-methylpyridine (1.0 g, 4 mmol) were placed in a 100 mL round-bottom flask. 20 mL of a 50:50 solution of ethanol and methanol was added to the flask. The reaction mixture was refluxed for 8 hours. The reaction mixture was then cooled to room temperature. The reaction mixture was poured onto a short silica column and washed with ethanol followed by hexane. The filtrate was discarded. The short column was then washed with dichloromethane to elute the product. The solvent was removed from the filtrate using a rotary evaporator. The product was further purified by column chromatography using a 50:50 solution of dichloromethane and hexane as eluents, yielding 0.5 g (50% yield) of the product.

[0178] Example 5: Synthesis of Compound 50

[0179]

[0180] Synthesis of Compound 50. Iridium trifluoromethanesulfonate complex (6.58 g, 9.2 mmol) and 4-(ethyl, d3)-2,5-diphenylpyridine (6.58 g, 25.0 mmol) were placed in a 1000 mL round-bottom flask. 140 mL of a 50:50 solution of ethanol and methanol was added to the flask. The reaction mixture was refluxed for 8 hours. The reaction mixture was then cooled to room temperature. The reaction mixture was poured onto a short silica column and washed with ethanol followed by hexane. The filtrate was discarded. The short column was then washed with dichloromethane to elute the product. The solvent was removed from the filtrate using a rotary evaporator. The product was further purified by column chromatography using a 50:50 solution of dichloromethane and hexane as eluents, yielding 3.8 g (54% yield) of product.

[0181] Device Examples

[0182] All devices pass through a high vacuum (<10) -7 The process is carried out by thermal evaporation (Tor). The anode is... Indium tin oxide (ITO). The cathode is made of... LiF and subsequent The components are composed of Al. All devices were immediately sealed in a nitrogen glove box (<1 ppm H₂O and O₂) with an epoxy-sealed glass lid and a desiccant was added to the packaging after fabrication.

[0183] Specific devices are provided in which the compounds of the present invention, namely compounds 10, 13, and 27, are luminescent dopants, and H1 is the host. In all device embodiments, the organic stack, starting from the ITO surface, consists of a hole injection layer (HIL) and... E1, as the hole transport layer (HTL) 4,4'-Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD), as a light-emitting layer (EML) The host material H1, doped with 7% or 10% of the compound of the present invention, serves as a barrier layer (BL). H1 and as ETL Composition of Alq3 (tri-8-hydroxyquinoline aluminum).

[0184] Comparative Examples 1-5 were fabricated in a similar manner to the device examples, except that the materials used in the EML and BL were different. Specifically, E1, E2, or E3 were used as the luminescent dopant in the EML of Comparative Examples 1 and 2, 3, 4, and 5, respectively. Furthermore, HPT was the BL material used in Comparative Example 3.

[0185] As used herein, the following compounds have the following structures:

[0186]

[0187] Specific materials for use in OLEDs are provided. In particular, these materials can be used as light-emitting dopants in the emissive layer (EML) of such devices. The compounds provided herein can be used to improve lifetime, efficiency, and color in devices.

[0188] Table 2

[0189]

[0190] Table 3

[0191]

[0192] As can be seen from device examples 1-6, the CD3 compound provided herein as a light-emitting dopant offers a long lifetime. In particular, the lifetime RT of the device examples containing the provided compound... 80％ (defined at 40mA / cm) 2 The time required for the initial luminance L0 to decay to 80% of its value at a constant current density and at room temperature was significantly longer than that of the comparative examples containing the corresponding CH3-substituted compounds. Specifically, compound 13 used in device examples 3 and 4 provided RTs of 204 hours and 220 hours, respectively. 80％ In contrast, the RT of Comparative Examples 1 and 3 using the corresponding CH3-substituted compound (E1) 80％ The options are 165 hours and 155 hours.

[0193] The data above also demonstrate that the CD3-containing heterocoordination compounds presented herein can provide devices with improved lifetime and efficiency. In particular, devices in Examples 5 and 6 containing compound 27 provide better lifetime and efficiency compared to comparative Examples 4 and 5 containing the corresponding CH3-substituted compound (E3). Specifically, compound 27 provides 174 hours and 184 hours of response time (RT), respectively. 80％ In contrast, the RT of the corresponding methyl-substituted compound E3 80％ The times are 116 hours and 128 hours.

[0194] Furthermore, the methyl-d3 substituted compounds provide devices with improved efficiency. In particular, compounds 10, 13, and 27 achieve lower operating voltages than comparative examples using the corresponding CH3-substituted compounds. Specifically, compounds 10, 13, and 27 provide operating voltages (V) of 5.2V, 5.6V, and 4.9V, respectively, relative to 6.4V, 5.8V, and 5.1V.

[0195] The data above demonstrate that the methyl-d3-substituted compounds presented in this paper can be excellent luminescent dopants for phosphorescent OLEDs. These compounds provide devices with improved color, efficiency, and lifetime.

[0196] As used herein, the following compounds have the following structures:

[0197]

[0198] Table 4

[0199]

[0200] Table 5

[0201]

[0202] As can be seen from devices 7 and 8, compound 43 exhibits comparable efficiency and color to E4, and a significantly longer device lifetime. Device 7 demonstrates a lifetime of 374 hours. 80 In contrast, Comparative Example 6 exhibited a lifetime of 212 hours. Device Example 8 exhibited a lifetime of 365 hours. 80 In contrast, Comparative Example 7 exhibited a lifetime of 283 hours. Device data indicate that the provided methyl-d3-substituted compound can improve device lifetime.

[0203] It should be 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 substituted with other materials and structures without departing from the spirit of the invention. Therefore, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein that will be obvious to those skilled in the art. It should be understood that the various theories regarding why the invention is possible are non-limiting.

Claims

1. An organic light-emitting device, comprising: anode cathode; and An organic layer located between the anode and the cathode, wherein the organic layer comprises compounds selected from the following compounds: 。 2. The device according to claim 1, wherein the organic layer is a light-emitting layer, and the compound is a light-emitting dopant.

3. The device according to claim 2, wherein the organic layer further comprises a host.

4. A consumer product comprising the device according to any one of claims 1 to 3.

5. The consumer product according to claim 4, wherein the product is selected from flat panel displays, fully transparent displays, and flexible displays.

6. The consumer product of claim 4, wherein the product is selected from computer monitors, televisions, hazard warning displays, laptops, and laser printers.

7. The consumer product according to claim 4, wherein the product is selected from telephones, personal digital assistants, digital cameras, portable video cameras, viewfinders, and miniature displays.

8. The consumer product according to claim 4, wherein it is a mobile phone.

9. The consumer product according to claim 4, wherein the product is selected from billboards, large-area walls, theater or stadium screens and signs.

10. The consumer product according to claim 4, wherein the product is selected from indoor or outdoor lighting.

11. The consumer product according to claim 4, wherein the product is selected from traffic lights and vehicles.

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