Organic electroluminescent materials and devices

Abstract

This invention relates to organic electroluminescent materials and devices. Novel ligands for metal complexes containing a five-membered ring fused to a pyridine or pyrimidine ring and combined with partially fluorinated side chains are disclosed, exhibiting improved external quantum efficiency and lifetime.

Description

[0001] This application is a divisional application of the invention patent application filed on May 13, 2016, with application number 201610318751.7 and entitled "Organic Electroluminescent Materials and Devices".

[0002] Cross-reference to related applications

[0003] This application is a non-provisional U.S. patent application that claims priority to U.S. Patent Application No. 62 / 161,948, filed May 15, 2015, pursuant to 35 U.S. SC §119(e)(1), the entire contents of which are incorporated herein by reference.

[0004] Parties to the Joint Research Agreement

[0005] The claimed invention was made by one or more of the following parties who entered into a joint university-corporation research agreement, in the name of one or more of the following parties and / or in conjunction with one or more of the following parties: the University of Michigan Board of Trustees, Princeton University, the University of Southern California, and Universal Display Corporation. The agreement was effective on or 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 agreement. Technical Field

[0006] The present invention relates to compounds suitable for use as emitters; and devices including the same, such as organic light-emitting diodes. Background Technology

[0007] Optoelectronic devices utilizing organic materials are becoming increasingly popular for several reasons. Many of the materials used to manufacture such devices are relatively inexpensive, thus organic optoelectronic devices have the potential to achieve a 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 diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials. For instance, the wavelength of light emitted by an organic emitting layer can often be easily tuned using appropriate dopants.

[0008] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly prominent technology for applications such as flat panel displays, lighting, and backlighting. Several OLED materials and configurations are described in U.S. Patents 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0009] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suitable for emitting specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single EML devices or stacked structures. Color can be measured using CIE coordinates, well known in the art.

[0010] An example of a green emitting molecule is tris(2-phenylpyridine)iridium, denoted as Ir(ppy)3, which has the following structure:

[0011]

[0012] In this structure and the structures that follow in this paper, the valence bond from nitrogen to the metal (here, Ir) is depicted as a straight line.

[0013] As used herein, the term "organic" includes polymeric materials as well as small-molecule organic materials that can be used to manufacture organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and "small molecule" can actually be quite large. In some cases, small molecules can include repeating units. For example, using long-chain alkyl groups as substituents does not remove the molecule from the "small molecule" category. Small molecules can also be incorporated into polymers, for example, as side groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core portion of dendritic polymers, which consist of a series of chemical shells built upon the core portion. The core portion of a dendritic polymer can be a fluorescent or phosphorescent small-molecule emitter. Dendritic polymers can be "small molecules," and it is believed that all dendritic polymers currently used in the OLED field are small molecules.

[0014] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. When the first layer is described as being "placed" "on" the second layer, the first layer is positioned further from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even if various organic layers exist between the cathode and anode, the cathode may still be described as being "placed" "on" the anode.

[0015] As used herein, “solution-handleable” means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0016] When a ligand is believed to directly contribute to the photosensitivity of the emitting material, the ligand can be called "photosensitive." When a ligand is believed not to contribute to the photosensitivity of the emitting material, the ligand can be called "auxiliary," but auxiliary ligands can alter the properties of photosensitivity ligands.

[0017] As used herein, and as will be understood by those skilled in the art, if a first energy level is closer to the vacuum level, then the first “highest occupied molecular orbital” (HOMO) or “lowest unoccupied molecular orbital” (LUMO) level is “greater” or “higher” than the second HOMO or LUMO level. Since the 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 (less negative IP). Similarly, a higher LUMO level corresponds to a smaller absolute value of electron affinity (EA) (less 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. A “higher” HOMO or LUMO level appears to be closer to the top of this diagram than a “lower” HOMO or LUMO level.

[0018] As used herein, and as will be understood by those skilled in the art, if the first work function has a higher absolute value, then the first work function is “greater” or “higher” than the second work function. This is because work functions are typically measured as negative numbers relative to the vacuum level, thus implying that the “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 described as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow a different convention than those for work functions.

[0019] Further details regarding OLEDs and the definitions described above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety. Summary of the Invention

[0020] According to some embodiments of the present invention, a compound is disclosed that comprises a ligand L of formula I.A ,

[0021] Where ring A is a 5- or 6-membered carbon ring or a heterocyclic ring;

[0022] Where R is fused to ring B and has the structure of formula II:

[0023]

[0024] The wavy lines represent the bond with ring B;

[0025] Where R 1 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted groups;

[0026] Where R 2 Indicates a single substituent, a disubstituent, or no substituent;

[0027] Where X 1 X 2 X 3 and X 4 Each is either carbon or nitrogen;

[0028] At least two adjacent X 1 X 2 X 3 and X 4 It is carbon and fused to R;

[0029] X is selected from the following groups: BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R".

[0030] Where R 1 R 2 R 3 R 4 R' and R" are each independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any two adjacent substituents are optionally linked to form a ring;

[0031] Where R 3 and R 4 At least one of them contains a chemical group selected from the group consisting of: alkyl, cycloalkyl, partially fluorinated alkyl, partially fluorinated cycloalkyl and combinations thereof;

[0032] The ligand L A Coordination to metal M;

[0033] The ligand L A Optionally linked with other ligands to include tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0034] M can be selectively coordinated to other ligands.

[0035] According to some embodiments, a first OLED is disclosed, comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a ligand L comprising formula I. A Compounds.

[0036] According to some embodiments, a formulation comprising a ligand L of formula I is also disclosed. A Compounds. Attached Figure Description

[0037] Figure 1 An organic light-emitting device was displayed.

[0038] Figure 2 An inverted organic light-emitting device without a separate electron transport layer was demonstrated. Detailed Implementation

[0039] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer at the cathode. The injected holes and electrons migrate toward the electrodes with opposite charges. When electrons and holes are confined to the same molecule, "excitons" are formed, which are localized electron-hole pairs with excited energy states. When excitons relax via photoemission mechanisms, light is emitted. In some cases, excitons may be confined to polarons or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0040] Early OLEDs used emitting molecules that emitted light from a single state (“fluorescence”), as disclosed, for example, in U.S. Patent No. 4,769,292, which is incorporated herein by reference in its entirety. Fluorescence emission typically occurs in timeframes of less than 10 nanoseconds.

[0041] Recently, OLEDs with emitting materials that emit light from the triplet state (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, Vol. 395, pp. 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, pp. 4–6 (1999) (“Baldo-II”), are incorporated herein by reference in their entirety. Phosphorescence is described in more detail in columns 5–6 of U.S. Patent No. 7,279,704, which is incorporated herein by reference.

[0042] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of these various layers, as well as the example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0043] There are numerous examples of each of these layers. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of emitter and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes are disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. These cathodes comprise composite cathodes having a thin metal layer, such as Mg:Ag, overlaid with a transparent, conductive, sputter-deposited ITO layer. The principles 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, which are also incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is also incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is also incorporated herein by reference in its entirety.

[0044] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emitter layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by sequentially depositing the layers described herein. Because the most common OLED configuration has a cathode disposed on the anode, and the device 200 has a cathode 215 disposed beneath the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of the device 200. Figure 2 An example is provided of how some layers can be omitted from the structure of device 100.

[0045] Figure 1 and 2The simple layered structures described herein are provided as non-limiting examples, and it should be understood that embodiments of the invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. A functional OLED can be realized by combining the described layers in different ways based on design, performance, and cost factors, or several layers can be omitted entirely. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials (e.g., mixtures of host and dopant) or more generally, mixtures may be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emitter layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, regarding Figure 1 and 2 Multiple layers of different organic materials are described.

[0046] Structures and materials not specifically described can also be used, such as OLEDs (PLEDs) containing polymeric materials, as disclosed in, for example, U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. As another example, an OLED with a single organic layer can be used. OLEDs can be stacked, as described, for example, in No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure can be detached... Figure 1 and 2 The simple layered structure described herein. For example, the substrate may include angled reflective surfaces to improve out-coupling, such as the tabletop structure as described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure as described in U.S. Patent No. 5,834,893 to Bulovic et al., all of which are incorporated herein by reference in their entirety.

[0047] Unless otherwise specified, any of the layers in the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (e.g., as described in U.S. Patent Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor deposition (OVPD) (e.g., as described in U.S. Patent No. 6,337,102 to Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (e.g., as described in U.S. Patent No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition via a mask, cold soldering (e.g., as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet printing and OVJD. Other methods may also be used. The material to be deposited can be modified to make it compatible with a specific deposition method. For example, substituents such as alkyl and aryl groups, which are branched or unbranched and preferably contain at least three carbons, can be used in small molecules to enhance their solution handling ability. Substituents having 20 or more carbons can be used, with 3-20 carbons being a preferred range. Materials with asymmetric structures can have better solution handling ability than materials with symmetric structures because asymmetric materials can have a lower tendency to recrystallize. Dendritic polymer substituents can be used to enhance the solution handling ability of small molecules.

[0048] Devices manufactured according to embodiments of the present invention may optionally further include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in the environment, including moisture, vapors, and / or gases. The barrier layer may be deposited on, under, or adjacent to a substrate or electrode, or on any other part of the device, including edges. The barrier layer may comprise a single layer or multiple layers. The barrier layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic or organic compounds, or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. Patent No. 7,968,146, PCT Patent Application Nos. PCT / US2007 / 023098 and PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. For the mixture to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited under the same reaction conditions and / or simultaneously. The weight ratio of polymeric material to non-polymeric material can range from 95:5 to 5:95. The polymeric and non-polymeric materials can be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0049] Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into various electronic products or intermediate components. Examples of such electronic products or intermediate components include displays, lighting devices (such as discrete light source devices or lighting panels), etc., which can be utilized by end-user product manufacturers. Such electronic component modules may optionally include driving electronics and / or power supplies. Devices manufactured according to embodiments of the present invention can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Such consumer products will include any kind of product containing one or more light sources and / or one or more of some type of visual display. Examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, mobile phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, miniature displays, 3D displays, vehicles, large-area walls, theater or stadium screens, or signs. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to the invention. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18 to 30 degrees Celsius, and more preferably at room temperature (20-25 degrees Celsius), but can be used outside this temperature range (e.g., -40 to +80 degrees Celsius).

[0050] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. More generally, organic devices such as organic transistors can use the materials and structures.

[0051] As used herein, the terms “halogen,” “halogen,” or “halogen” include fluorine, chlorine, bromine, and iodine.

[0052] As used herein, the term "alkyl" encompasses both straight-chain and branched alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, and include 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, etc. Additionally, the alkyl group may optionally be substituted.

[0053] As used herein, the term "cycloalkyl" encompasses cyclic alkyl groups. Preferred cycloalkyl groups are those containing 3 to 10 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may optionally be substituted.

[0054] As used herein, the term "alkenyl" encompasses both straight-chain and branched alkenyl groups. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl groups may optionally be substituted.

[0055] As used herein, the term "alkynyl" encompasses both straight-chain and branched alkynyl groups. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0056] As used herein, the terms “aralkyl” or “arylalkyl” are used interchangeably and cover alkyl groups having aromatic groups as substituents. Additionally, aralkyl groups may optionally be substituted.

[0057] As used herein, the term "heterocyclic group" encompasses both aromatic and non-aromatic cyclic groups. Heteroaromatic cyclic groups also refer to heteroaryl groups. Preferred heterocyclic non-aromatic cyclic groups are heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines such as morpholino, piperidinyl, pyrrolyl, etc., and cyclic ethers such as tetrahydrofuran, tetrahydropyran, etc. Furthermore, the heterocyclic group may optionally be substituted.

[0058] As used herein, the term "aryl" or "aromatic group" encompasses both monocyclic groups and polycyclic systems. A polycyclic system may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is aromatic; for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, leucine, perylene, and azulene, with phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene being preferred. Additionally, the aryl group may optionally be substituted.

[0059] As used herein, the term "heteroaryl" encompasses a monocyclic heteroaryl aromatic group that may include one to five heteroatoms. The term "heteroaryl" also includes polycyclic heteroaryl aromatic systems having two or more rings shared by two adjacent rings (the rings being "fused"), wherein at least one of the rings is a heteroaryl, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indoleazine, benzoxazole, and benziisobenzyl. Oxazoles, benzothiazoles, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenotoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0060] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic, aryl, and heteroaryl groups may be unsubstituted or may be substituted by one or more substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0061] As used in this article, "substituted" means that the substituent is not H bonded to the relevant position, such as carbon. Therefore, for example, in R... 1 When replaced by a single unit, then an R 1 It must not be H. Similarly, in R... 1 When replaced by two, then the two Rs 1 It must not be H. Similarly, in R... 1 When not replaced, R 1 It is hydrogen for all available locations.

[0062] The term "aza" in the fragments described herein (i.e., aza-dibenzofuran, aza-dibenzothiophene, etc.) indicates that one or more CH groups in the individual fragment can be substituted with nitrogen atoms. For example, and without limitation, azatriphenylene covers dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily contemplated by those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0063] It should be understood that when a molecular fragment is described as a substituent or additionally attached to another part, its name can be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0064] According to one aspect of the invention, ligands comprising a five-membered ring fused to a pyridine or pyrimidine ring and combined with a partially fluorinated side chain are disclosed, and are found to be suitable for use in phosphorescent metal complexes for organic light-emitting devices. The resulting luminescent metal complexes exhibit improved external quantum efficiency and lifetime.

[0065] Some exemplary ligands disclosed herein are fluoropyrimidine, thienopyrimidine, pyrrolopyrimidine, and cyclopentanopyrimidine. In some embodiments, these ligands may be combined with an aliphatic substituent containing at least one F atom. Combinations of these two moieties on a single ligand are used for a variety of reasons. Pyridine- or pyrimidine-based ligands for red dopants have shown excellent device efficiency and good lifetime. Incorporating one or more side chains containing F atoms will allow for fine-tuning of the color and, in particular, provide a redshift.

[0066] According to some embodiments, a compound is disclosed that comprises a ligand L of formula I. A , Where ring A is a 5- or 6-membered carbon ring or a heterocyclic ring;

[0067] R is fused to ring B and has the structure of formula II. The wavy lines represent the bond with ring B;

[0068] Where R 1 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted groups;

[0069] Where R 2 Indicates a single substituent, a disubstituent, or no substituent;

[0070] Where X 1 X 2 X 3 and X4 Each is either carbon or nitrogen;

[0071] At least two adjacent X 1 X 2 X 3 and X 4 It is carbon and fused to R;

[0072] X is selected from the following groups: BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R".

[0073] Where R 1 R 2 R 3 R 4 R' and R" are each independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any two adjacent substituents are optionally linked to form a ring;

[0074] Where R 3 and R 4 At least one of them contains a chemical group selected from the group consisting of: alkyl, cycloalkyl, partially fluorinated alkyl, partially fluorinated cycloalkyl and combinations thereof;

[0075] The ligand L A Coordination to metal M;

[0076] The ligand L A Optionally linked to other ligands to include tridentate, tetradentate, pentadentate, or hexadentate ligands; and wherein M is optionally coordinated to other ligands.

[0077] In some embodiments of the compound, M is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Au, and Cu.

[0078] In some embodiments of the compound, M is Ir or Pt.

[0079] In some embodiments of the compound, the ligand L A Choose from the following groups:

[0080]

[0081] In some embodiments of the compound, the ligand L A yes:

[0082]

[0083] In some embodiments of the compound, the ligand L A yes:

[0084]

[0085] In some embodiments of the compound, R 3 and R 4 At least one of them is a chemical group selected from the group consisting of: alkyl, cycloalkyl, partially fluorinated alkyl, partially fluorinated cycloalkyl, and combinations thereof.

[0086] In some embodiments of the compound, R 3 and R 4 At least one of them is a chemical group selected from the group consisting of: partially fluorinated alkyl groups, partially fluorinated cycloalkyl groups, and combinations thereof.

[0087] In some embodiments of the compound, R 3 and R 4 It's not hydrogen.

[0088] In some embodiments of the compound, X 1 X 2 X 3 and X 4 At least one of them is nitrogen.

[0089] In some embodiments of the compound, X is O.

[0090] In some embodiments of the compound, X is NR'.

[0091] In some embodiments of the compound, X is CR'R″ or SiR'R″.

[0092] In some embodiments of the compound, R 1 R 2 R 3 R 4 R' and R″ are each independently selected from the following groups: hydrogen, deuterium, alkyl, cycloalkyl and combinations thereof.

[0093] In some embodiments of the compound, R 1 R 2 R 3 R 4R' and R″ are each independently selected from the group consisting of: hydrogen, deuterium, 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 and combinations thereof.

[0094] In some embodiments of the compound, R 3 and R 4 At least one of them is selected from the following groups:

[0095]

[0096]

[0097] In some embodiments of the compound, R 3 With R 4 Connect to form a ring structure selected from the following groups:

[0098]

[0099] In some embodiments of the compound, R 3 and R 4 At least one of them is selected from the following groups:

[0100] In some embodiments of the compound, the ligand L A Choose from the following groups:

[0101] Where R 1 R 3 R 4 R' is as defined above.

[0102] In some embodiments of the compound, the ligand L A Choose from the following groups: L as defined below A1 To L A750 :

[0103] L A1 To L A375 Based on the structure of Form IV, Where R 3 R 4 X is defined as shown in Table 1 below:

[0104] Table 1

[0105]

[0106]

[0107]

[0108]

[0109] And L A376 To L A750 Based on the structure of formula V, Where R 3 R 4 X is defined as shown in Table 2 below:

[0110] Table 2

[0111]

[0112]

[0113]

[0114] Where R B1 To R B4 It has the following structure:

[0115] In some embodiments of the compound, the compound has the structure of Formula III, (L A ) n Ir(L B ) 3-n L B It is a bidentate ligand and n is 1, 2 or 3.

[0116] In some embodiments of compounds having the structure of Formula III, the ligand L B Choose from the following groups:

[0117]

[0118] In some embodiments of compounds having the structure of Formula III, the compounds are selected from the group consisting of compounds 1 to 12,750;

[0119] Each compound x has the formula Ir(L Ak )2(L Bj );

[0120] Where x = 750j + k - 750, k is an integer from 1 to 750, and j is an integer from 1 to 17; and where the ligand L B1 To L B17 The definition is as follows:

[0121]

[0122] In some embodiments of the compound, the compound has the structure of formula VI, (L A ) m Pt(L C ) 2-m L C It is a bidentate ligand, and m is 1 or 2.

[0123] In some embodiments of compounds having the structure of formula VI, m is 1, and L A Connect to L C To form a tetradentate ligand.

[0124] According to another aspect of the present invention, a first organic light-emitting device is disclosed, comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer includes a ligand L comprising formula I. A compounds, Where ring A is a 5- or 6-membered carbon ring or a heterocyclic ring;

[0125] R is fused to ring B and has the structure of formula II. The wavy lines represent the bond with ring B;

[0126] Where R 1 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted groups;

[0127] Where R 2 Indicates a single substituent, a disubstituent, or no substituent;

[0128] Where X 1 X 2 X 3 and X 4 Each is either carbon or nitrogen;

[0129] At least two adjacent X 1 X 2 X 3 and X 4 It is carbon and fused to R;

[0130] X is selected from the following groups: BR', NR', PR', O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", and GeR'R".

[0131] Where R 1 R 2 R 3 R 4R' and R" are each independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and any two adjacent substituents are optionally linked to form a ring;

[0132] Where R 3 and R 4 At least one of them contains a chemical group selected from the group consisting of: alkyl, cycloalkyl, partially fluorinated alkyl, partially fluorinated cycloalkyl and combinations thereof;

[0133] Where L A Coordination to metal M;

[0134] Where L A Optionally linked with other ligands to include tridentate, tetradentate, pentadentate, or hexadentate ligands; and

[0135] M can be selectively coordinated to other ligands.

[0136] The organic light-emitting devices disclosed herein can be incorporated into one or more of the following: consumer products, electronic component modules, organic light-emitting devices, and lighting panels. The organic layer may be an emitting layer, and the compound may be an emitting dopant in some embodiments, while in other embodiments it may be a non-emitting dopant.

[0137] The organic layer may further include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the host used may be a) bipolar, b) electron transport, c) hole transport, or d) wide bandgap material that plays a minimal role in charge transport. In some embodiments, the host may include a metal complex. The host may be triphenylene containing benzofused thiophene or benzofused furan. Any substituent in the host may be a non-fused substituent independently selected from the group consisting of: C n H 2n+1 OC n H 2n+1 ,OAr1,N(C n H 2n+1 2. N(Ar1)(Ar2), CH=CH-C n H 2n+1 C≡CC n H 2n+1 Ar1, Ar1-Ar2 and C n H 2n-Ar1, or the host cell may not have any substituents. In the aforementioned substituents, n can vary from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and their heteroaromatic analogs. The host cell may be an inorganic compound. For example, a Zn-containing inorganic material, such as ZnS.

[0138] The host may be a compound comprising at least one chemical group selected from the group consisting of: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenene. The host may include a metal complex.

[0139] The subject can be (but is not limited to) a specific compound selected from the group consisting of:

[0140] And their combinations. Additional information about possible entities is provided below.

[0141] According to another aspect of the invention, a formulation is disclosed comprising a ligand L of inclusion formula I as defined above. A The compound may include one or more components selected from the group consisting of solvents, host materials, hole injection materials, hole transport materials, and electron transport layer materials disclosed herein.

[0142] Combination with other materials

[0143] 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 said devices. For example, the emission dopants disclosed herein can be used in combination with a variety of host layers, transport layers, barrier layers, injection layers, electrodes, and other possible layers. The materials described or mentioned 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.

[0144] Conductive dopants:

[0145] The charge transport layer can be doped with conductive dopants to substantially alter its charge carrier density, which in turn changes its conductivity. Conductivity is increased by generating charge carriers in the matrix material and, depending on the type of dopant, can also achieve changes in the Fermi level of the semiconductor. Hole transport layers can be doped with p-type conductive dopants, and n-type conductive dopants are used in electron transport layers. Non-limiting examples of conductive dopants that can be used in combination with the materials disclosed herein for OLEDs are illustrated below, along with the references to those materials:

[0146] EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

[0147]

[0148] HIL / HTL:

[0149] The hole injection / delivery materials used in this invention are not particularly limited, and any compound can be used, provided that the compound is typically used as a hole injection / delivery material. Examples of such materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indole-carbazole derivatives; polymers containing fluorinated hydrocarbons; polymers with conductive dopants; conductive polymers, such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; and metal oxide derivatives, such as MoO. x p-type semiconductor organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes, and crosslinkable compounds.

[0150] Examples of aromatic amine derivatives used in HILs or HTLs include (but are not limited to) the following general formula structures:

[0151]

[0152] Ar 1 To Ar 9Each of these is selected from the group consisting of aromatic cyclic hydrocarbons, such as benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, olean, perylene, and azulene; and from the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, indolodiazole Azides, benzoxazoles, benzoisoxazoles, benzothiazoles, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and a group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0153] In one respect, Ar 1 To Ar 9 Choose independently from the following groups:

[0154]

[0155] Where k is an integer from 1 to 20; X 101 To X 108 It is C (including CH) or N; Z 101 It is NAr 1 , O or S; Ar 1 Having the same functional groups as defined above.

[0156] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0157]

[0158] Met is a metal that can have an atomic weight greater than 40; (Y 101 -Y 102) is a bidentate ligand, Y 101 and Y 102 Independently selected from C, N, O, P, and S; L 101 It is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0159] In one respect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. On the other hand, (Y) 101 -Y 102 Met is a carbapenem ligand. On the other hand, Met is selected from Ir, Pt, Os, and Zn. On the other hand, the metal complex has a relative voltage of less than about 0.6 V with respect to Fc. + The minimum oxidation potential in solution for / Fc pairs.

[0160] Non-limiting examples of HIL and HTL materials for OLEDs that can be combined with the materials disclosed herein are illustrated below, along with the references that disclose those materials:

[0161] CN102702075、DE102012005215、EP01624500、EP01698613、EP01806334、EP01930964、EP01972613、EP01997799、EP02011790、EP02055700、EP02055701、EP1725079、EP2085382、EP2660300、EP650955、JP07-073529、JP2005112765、JP2007091719、JP2008021687、JP2014-009196、KR20110088898、KR20130077473、TW201139402、US06517957、US20020158242、US20030162053、US20050123751、US20060182993、US20060240279、US20070145888、US20070181874、US20070278938、US20080014464、US20080091025、US20080106190、US20080124572、US20080145707、US20080220265、US20080233434、US20080303417、US2008107919、US20090115320、US20090167161、US2009066235、US2011007385、US20110163302、US2011240968、US2011278551、US2012205642、US2013241401、US20140117329、US2014183517、US5061569、US5639914、WO05075451、WO07125714、WO08023550、WO08023759、WO2009145016、WO2010061824、WO2011075644、WO2012177006、WO2013018530、WO2013039073、WO2013087142、WO2013118812、WO2013120577、WO2013157367、WO2013175747、WO2014002873、WO2014015935、WO2014015937、WO2014030872、WO2014030921、WO2014034791、WO2014104514、WO2014157018。

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] EBL:

[0169] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and / or higher triplet energy compared to the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO and / or higher triplet energy compared to one or more of the bodies closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecules or the same functional groups as those used in one of the bodies described below.

[0170] main body:

[0171] The light-emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as the light-emitting material, and may contain a host material using a metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used, as long as the triplet energy of the host is greater than that of the dopant. Although the table below categorizes host materials preferred for emitting various colors, any host material can be used with any dopant, provided the triplet criterion is satisfied.

[0172] Examples of metal complexes used as the host preferably have the following general formula:

[0173]

[0174] Where Met is a metal; (Y) 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 Independently selected from C, N, O, P, and S; L 101It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k'+k" is the maximum number of ligands that can be connected to the metal.

[0175] In one respect, metal complexes are:

[0176]

[0177] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0178] On the other hand, Met is selected from Ir and Pt. On the other hand, (Y 103 -Y 104 ) is a carbaene ligand.

[0179] Examples of organic compounds used as the host are selected from the group consisting of aromatic hydrocarbon ring compounds, such as benzene, biphenyl, biphenylene, triphenylene, tetraphenylene, naphthalene, anthracene, fennel, fluorene, pyrene, olean, perylene, and azulene; and the group consisting of aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenene, furan, thiophene, benzofuran, benzothiophene, benzoselenene, carbazole, indolocarbazole, pyridinylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indole, and indole. The group consisting of azoles, indoxaazines, benzoxazoles, benzoisoxaazoles, benzothiazolium, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, dibenzopiperan, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selelene-dipyridine; and the group consisting of 2 to 10 cyclic structural units, said structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups, and being bonded to each other directly or via at least one of oxygen, nitrogen, sulfur, silicon, phosphorus, boron, chain structural units, and aliphatic cyclic groups. Each choice within each group may be unsubstituted or may be substituted by substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0180] In one respect, the host compound contains at least one of the following groups in its molecule:

[0181]

[0182] Where R101 To R 107 Each of these is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to that of Ar above. k is an integer from 0 to 20 or from 1 to 20; k'" is an integer from 0 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0183] Z 101 and Z 102 Selected from NR 101 、O or S.

[0184] Non-limiting examples of bulk materials for OLEDs that can be used in conjunction with the materials disclosed herein, along with references to those materials, are illustrated below:

[0185] EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR201301 15564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090 167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US201 2075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US201402 25088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, W O2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO200 9066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128 298. WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472.

[0186]

[0187]

[0188]

[0189]

[0190]

[0191] Launcher:

[0192] The examples of emitters are not particularly limited, and any compound can be used, as long as it is typically used as an emitter material. Examples of suitable emitter materials include (but are not limited to) compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0193] Non-limiting examples of emitter materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR2012003 2054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US 20050123788, US20050244673, US2005123791, US2005260449, US20060008 670、US20060065890、US20060127696、US20060134459、US20060134462、US2 0060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] HBL:

[0201] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, the blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (farthest from vacuum level) and / or higher triplet energy compared to the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO and / or higher triplet energy compared to one or more of the bodies closest to the HBL interface.

[0202] In one respect, the compounds used in HBL contain the same molecules or the same functional groups used as the aforementioned main body.

[0203] On the other hand, the compounds used in HBL contain at least one of the following groups in their molecules:

[0204]

[0205] Where k is an integer from 1 to 20; L 101 It is another ligand, and k' is an integer from 1 to 3.

[0206] ETL:

[0207] An electron transport layer (ETL) can comprise a material capable of transporting electrons. The ETL can be intrinsic (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 can be used, as long as it is typically used for electron transport.

[0208] In one respect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0209]

[0210] Where R 101 The group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphine, and combinations thereof, when it is aryl or heteroaryl, has a similar definition to Ar as described above.1 To Ar 3 It has a similar definition to Ar above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0211] On the other hand, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0212]

[0213] Wherein (ON) or (NN) are bidentate ligands of a metal that coordinate with atoms O, N or N, N; L 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bonded to a metal.

[0214] Non-limiting examples of ETL materials for OLEDs that can be used in conjunction with the material combinations disclosed herein are illustrated below, along with references to those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US20 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535.

[0215]

[0216]

[0217]

[0218] Charge generation layer (CGL)

[0219] In tandem or stacked OLEDs, the conduction layer (CGL) plays a fundamental role in performance. It consists of an n-doped layer and a p-doped layer, respectively, for injecting electrons and holes. Electrons and holes are supplied by the CGL and the electrodes. Electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductive dopants used in the transport layer.

[0220] In any of the compounds described above used in each layer of an OLED device, hydrogen atoms may be partially or fully deuterated. Therefore, any specifically listed substituent (e.g., but not limited to, methyl, phenyl, pyridyl, etc.) may be in its undeuterated, partially deuterated, or fully deuterated form. Similarly, substituent classes (e.g., but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their undeuterated, partially deuterated, or fully deuterated forms.

[0221] experiment

[0222] Material synthesis

[0223] Unless otherwise specified, all reactions are carried out under nitrogen protection. All solvents used in the reactions are anhydrous and are commercially available and used as is.

[0224] Synthetic compound 3676

[0225] Synthesis of 4-(3,5-dimethylphenyl)-7-isopropylthiopheno[3,2-d]pyrimidine

[0226]

[0227] 4-Chloro-7-isopropylthiopheno[3,2-d]pyrimidine (4.50 g, 21.2 mmol), Pd(PPh3)4 (0.73 g, 0.64 mmol), potassium carbonate (7.31 g, 52.9 mmol), tetrahydrofuran (THF) (200 mL), and water (50.0 mL) were combined in a flask. The mixture was degassed by bubbling nitrogen for 15 minutes, and then the reaction mixture was heated to reflux overnight. The reaction mixture was extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated. The brown oil was purified with silica gel using a DCM to 90 / 10 DCM / ethyl acetate solvent system. The orange oil was further purified with silica gel using a 75 / 25 heptane / ethyl acetate solvent system to give 5.50 g of a white solid in 90% yield.

[0228] Synthesis of Ir(III) dimer

[0229]

[0230] 4-(3,5-dimethylphenyl)-7-isopropylthiopheno[3,2-d]pyrimidine (3.07 g, 10.9 mmol) was added to a flask and dissolved in 2-ethoxyethanol (40 mL) and water (13 mL). The mixture was degassed by bubbling nitrogen for 15 min, and then IrCl3H8O4 (1.15 g, 3.10 mmol) was added. The reaction mixture was heated at 105 °C under nitrogen for 24 h. The reaction mixture was cooled to room temperature, diluted with 10 mL of MeOH, filtered, and washed with MeOH to give 1.6 g of a solid in 65% yield.

[0231] Synthetic compound 3676

[0232]

[0233] Ir(III) dimer (1.00 g, 0.63 mmol), 3,7-diethylnon-4,6-dione (1.34 g, 6.33 mmol), and 2-ethoxyethanol (15 mL) were combined in a flask. Nitrogen was bubbled into the suspension for 15 minutes, and potassium carbonate (0.87 g, 6.33 mmol) was added. The reaction mixture was stirred overnight at room temperature. The mixture was filtered through diatomaceous earth using dichloromethane (DCM), and the filtrate was concentrated. The solid was ground in 100 mL of MeOH, and the solid was filtered off. The solid was purified with silica gel (pretreated with triethylamine) using 95 / 5 to 90 / 10 heptane / DCM to give 0.45 g of the title compound (37% yield).

[0234] Synthetic compound 6796

[0235] Synthesis of 6,7-dichloro-4-(3,5-dimethylphenyl)thiopheno[3,2-d]pyrimidine

[0236]

[0237] A mixture of 4,6,7-trichlorothiophene[3,2-d]pyrimidine (12.0 g, 50.1 mmol), (3,5-dimethylphenyl)boronic acid (8.27 g, 55.1 mmol), potassium carbonate (17.3 g, 125 mmol), THF (300 mL), and water (75 mL) was placed in a flask. The solution was purged with nitrogen for 15 min, and then tetrakis(triphenylphosphine)palladium (1.74 g, 1.503 mmol) was added. The reaction mixture was heated to reflux under nitrogen overnight. The reaction mixture was extracted with ethyl acetate (3 times) and then washed with brine and water. The yellow solid was purified with silica gel using a 90 / 10 heptane / EtOac solvent system to give a white solid. The sample was further purified with silica gel using a DCM to 95 / 5 DCM / EtOac solvent system to give 8.4 g of a white solid in 54% yield.

[0238] Synthesis of 4-(3,5-dimethylphenyl)-6,7-bis(3,3,3-trifluoropropyl)thiopheno[3,2-d]pyrimidine

[0239]

[0240] 6,7-Dichloro-4-(3,5-dimethylphenyl)thieno[3,2-d]pyrimidine (5.00 g, 16.2 mmol), palladium(II) acetate (0.73 g, 3.23 mmol), and 2'-(dicyclohexylphosphino)-N2,N2,N6,N6-tetramethyl-[1,1'-biphenyl]-2,6-diamine (CPhos) (2.82 g, 6.47 mmol) were combined in an oven-dried flask. The system was purged with nitrogen, and then THF (50 mL) was added using a syringe. The reaction mixture was stirred for 15 minutes, and then (3,3,3-trifluoropropyl)zinc(II) iodide (300 mL, 64.7 mmol) was rapidly added using a syringe. The reaction mixture was stirred overnight at room temperature and then quenched with sodium bicarbonate solution. The mixture was extracted three times with ethyl acetate, and the suspension was filtered through diatomaceous earth to remove insoluble solids. The organic phase was washed twice with brine, dried over sodium sulfate, filtered, and concentrated to a brown oil. The crude product was purified with silica gel using 90 / 10 heptane / ethyl acetate to give a light brown oil. The sample was further purified using a C18 column with a 70 / 30 to 90 / 10 acetonitrile / water solvent system to give 2.56 g of a white solid in a 37% yield.

[0241] Synthesis of Ir(III) dimer

[0242]

[0243] 4-(3,5-dimethylphenyl)-6,7-bis(3,3,3-trifluoropropyl)thieno[3,2-d]pyrimidine (2.86 g, 6.61 mmol), 2-ethoxyethanol (24 mL), and water (8 mL) were combined in a flask. Nitrogen gas was bubbled into the reactants for 15 minutes, and then IrCl3H8O4 (0.70 g, 1.89 mmol) was added. The reactants were heated overnight at 105 °C under nitrogen. The reactants were cooled, diluted with 10 mL of MeOH, filtered, and washed with MeOH to give 2.28 g (quantitative yield) of an orange-red solid.

[0244] Synthetic compound 6796

[0245]

[0246] Ir(III) dimer (2.10 g, 1.59 mmol), 3,7-diethyl-5-methylnonan-4,6-dione (4.0 mL, 15.9 mmol), and 2-ethoxyethanol (30 mL) were combined in a flask. Nitrogen was bubbled into the suspension for 15 minutes, and then potassium carbonate (2.20 g, 15.9 mmol) was added. The reaction mixture was stirred overnight at room temperature. After the reaction was complete, the reaction mixture was diluted in DCM and filtered through diatomaceous earth. The red oil was wet-milled in 75 mL of hot MeOH, cooled to room temperature, and then filtered. The solid was purified with silica gel (pretreated with triethylamine) using a 95 / 5 to 85 / 15 heptane / DCM solvent system to give 1.41 g of the title compound (35% yield).

[0247] Synthetic compound 6841

[0248] Synthesis of 6-bromo-4-(3,5-dimethylphenyl)-7-isopropylthiopheno[3,2-d]pyrimidine

[0249]

[0250] Add 4-(3,5-dimethylphenyl)-7-isopropylthiopheno[3,2-d]pyrimidine (5.00 g, 17.7 mmol) to an oven-dried flask. Evacuate the system and purge three times with nitrogen. Add THF (200 mL) and cool the solution to -70 °C, then add 2.5 M butyllithium (8.5 mL, 21.3 mmol) dropwise. Stir the reaction mixture at this temperature for three hours, then add dibromo (1.0 mL, 19.5 mmol) dropwise. Stir the reaction mixture at -70 °C for 30 minutes, then warm it to room temperature and stir overnight. Quench the mixture with water, extract with ethyl acetate, wash twice with brine, dry over sodium sulfate, filter, and concentrate to an orange-yellow solid. Purify the crude product with silica gel using a 95 / 5 to 90 / 10 heptane / EtOac solvent system to give a grayish-white solid. Repeated silica gel purification was performed using a 97.5 / 2.5 to 95 / 5 heptane / EtOac solvent system to give 5.10 g of a white solid in 80% yield.

[0251] Synthesis of 4-(3,5-dimethylphenyl)-7-isopropyl-6-(3,3,3-trifluoro-2,2-dimethylpropyl)thiopheno[3,2-d]pyrimidine

[0252]

[0253] 6-Bromo-4-(3,5-dimethylphenyl)-7-isopropylthiopheno[3,2-d]pyrimidine (4.50 g, 12.5 mmol), palladium(II) acetate (0.11 g, 0.50 mmol), and 2'-(dicyclohexylphosphino)-N2,N2,N6,N6-tetramethyl-[1,1'-biphenyl]-2,6-diamine (Cphos) (0.44 g, 1.00 mmol) were combined in an oven-dried flask. The solids were dissolved in THF (50 mL), and the mixture was stirred for 15 min. Then, (3,3,3-trifluoro-2,2-dimethylpropyl)zinc(II) bromide (110 mL, 24.9 mmol) was added using a syringe, and the mixture was stirred overnight. The mixture was quenched with sodium bicarbonate solution and extracted with ethyl acetate (3 times). The combined organic compounds were washed twice with brine, dried over sodium sulfate, filtered, and concentrated. The crude product was purified with silica gel using 85 / 15 heptane / ethyl acetate to give 5.0 g of brown oil. The product was then purified again with silica gel using 97.5 / 2.5 to 95 / 5 heptane / ethyl acetate to give 4.1 g of clear oil, which was then converted into a white solid in 80% yield.

[0254] Synthesis of Ir(III) dimer

[0255]

[0256] A mixture of 4-(3,5-dimethylphenyl)-7-isopropyl-6-(3,3,3-trifluoro-2,2-dimethylpropyl)thieno[3,2-d]pyrimidine (3.84 g, 9.44 mmol), 2-ethoxyethanol (34 mL), and water (11 mL) was placed in a flask. The mixture was degassed by bubbling nitrogen for 15 min, and then IrCl3H8O4 (1.00 g, 2.70 mmol) was added. The reaction mixture was heated at 105 °C for 24 h. The reaction mixture was cooled to room temperature, diluted with 30 mL of MeOH, and the product was filtered and washed with MeOH to give 2.50 g (quantitative yield).

[0257] Synthetic compound 6841

[0258]

[0259] Ir(III) dimer (2.00 g, 1.58 mmol), 3,7-diethyl-5-methylnonan-4,6-dione (3.58 g, 15.8 mmol), and 2-ethoxyethanol (30 mL) were combined in a flask. Nitrogen was bubbled into the suspension for 15 minutes, and then potassium carbonate (2.18 g, 15.8 mmol) was added. The reaction mixture was stirred overnight at room temperature. The mixture was filtered through diatomaceous earth using DCM, and the filtrate was concentrated. The solid was wet-milled in 100 mL of MeOH, and the solid was filtered off. The solid was purified with silica gel (pretreated with triethylamine) using 90 / 10 heptane / DCM to give 1.20 g of the title compound (31% yield).

[0260] Synthetic compound 6836

[0261]

[0262] Ir(III) dimer (1.80 g, 1.14 mmol), 3,7-diethyl-5-methylnonan-4,6-dione (2.9 mL, 11.4 mmol), and 2-ethoxyethanol (25 mL) were combined in a flask. Nitrogen was bubbled into the suspension for 15 minutes, and then potassium carbonate (1.57 g, 11.4 mmol) was added. The reaction mixture was stirred overnight at room temperature. The mixture was filtered through diatomaceous earth using DCM, and the filtrate was concentrated. The solid was wet-milled in 100 mL of MeOH and filtered off. The crude product was purified with silica gel (pretreated with triethylamine) using 95 / 5 to 90 / 10 heptane / DCM to give 1.20 g of the title compound (54% yield).

[0263] Synthesize Comparative Compound 1

[0264] Synthesis of Ir(III) dimer

[0265]

[0266] 7-(3,5-dimethylphenyl)thieno[2,3-c]pyridine (2.063 g, 8.62 mmol) was dissolved in ethoxyethanol (26 mL) and water (9 mL). The mixture was degassed by bubbling nitrogen for 15 min, and then iridium(III) chloride trihydrate (0.80 g, 2.269 mmol) was added, and the reaction mixture was heated at 105 °C for 24 h. The reaction mixture was cooled to room temperature, diluted with 10 mL of MeOH, filtered, and washed with MeOH to give 1.20 g (75% yield) of the product.

[0267] Synthesize Comparative Compound 1

[0268]

[0269] Ir(III) dimer (1.15 g, 0.82 mmol), 3,7-diethylnon-4,6-dione (1.30 g, 6.12 mmol), and 2-ethoxyethanol (14 mL) were combined, and the mixture was purged with nitrogen for 15 min. Potassium carbonate (0.85 g, 6.12 mmol) was added, and the reaction mixture was stirred overnight at room temperature. The mixture was dissolved in DCM and filtered through a diatomaceous earth pad. The solvent was rotary evaporated, and the mixture was wet-milled with methanol and filtered. The crude material was further purified by column chromatography (pretreated with triethylamine) using a heptane / DCM (95 / 5) solvent system. The product was then recrystallized from a DCM / MeOH mixture to give 1.30 g (90% yield) of orange powder.

[0270] Device Examples

[0271] All example devices were subjected to high vacuum (<10) -7 Manufactured by thermal evaporation. The anode electrode is... Indium tin oxide (ITO). The cathode is made of... Liq (lithium 8-hydroxyquinoline) followed by The device is composed of Al. Immediately after manufacturing, all devices are sealed in a nitrogen glove box (<1 ppm H₂O and O₂) with epoxy-sealed glass lids, and a desiccant is incorporated into the packaging. The organic stack of the device examples consists of the following components sequentially from the ITO surface: LG101 (purchased from LG Chem) was used as the hole injection layer (HIL); The HTM serves as the hole transport layer (HTL); The emitter layer (EML) contains compound H as the host, a stabilizing dopant (SD) (18%), and comparative compounds 1 or 3676, 6836 and 6841 as emitters (3%). Compound H serves as a barrier layer; and The device uses 40% ETM-doped Liq (lithium 8-hydroxyquinoline) as the ETL. The emitter is selected to provide the desired color, efficiency, and lifetime. A stabilizing dopant (SD) is added to the electron transport host to help transport positive charges in the emitter layer. A comparative example device was fabricated similar to the device example, except that comparative compound 1 was used as the emitter in the EML. Table 3 below shows the device layer thicknesses and materials. The chemical structures of the materials used in the device are shown in Table 5 below.

[0272] The device performance data are summarized in Table 4 below. The compounds of the present invention exhibit a significantly longer lifetime compared to comparative compound 1. Furthermore, compounds 3676, 6836, and 6841 demonstrate superior performance in color saturation compared to comparative compound 1, with a redshift of 28 to 38 nm observed. Moreover, the compounds of the present invention achieve similar or higher EQE compared to comparative compound 1.

[0273] Table 3. Materials and Thickness of Device Layers

[0274]

[0275] Table 4. Device Performance Data

[0276]

[0277] Table 5. Materials used in OLED devices

[0278]

[0279]

[0280] 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 instance, many of the materials and structures described herein can be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. A compound having the structure of Formula III (L A ) n Ir(L B ) 3-n L B It is a bidentate ligand and n is 2, where the ligand L A Choose from the following groups: , , , , and ; Where ring A is a benzene ring; Where R 1 This indicates monosubstituted, disubstituted, trisubstituted, tetrasubstituted, or unsubstituted groups; Where R 2 Indicates a single substituent, a disubstituent, or no substituent; X is selected from the following groups: O and S; Where R 1 R 2 R 3 and R 4 Each is independently selected from the following groups: hydrogen, deuterium, halogens, alkyl groups containing one to fifteen carbon atoms, cycloalkyl groups containing three to ten cyclic carbon atoms, amino groups, nitrile groups and combinations thereof; Where R 3 and R 4 At least one of them contains a chemical group selected from the group consisting of: alkyl groups containing one to fifteen carbon atoms, cycloalkyl groups containing three to ten cyclic carbon atoms, partially fluorinated alkyl groups containing one to fifteen carbon atoms, partially fluorinated cycloalkyl groups containing three to ten cyclic carbon atoms, and combinations thereof. The ligand L B Choose from the following groups: , , , , , , , , , , , , , , , and .

2. The compound according to claim 1, wherein R 3 and R 4 At least one of them is a chemical group selected from the group consisting of: partially fluorinated alkyl groups containing one to fifteen carbon atoms, partially fluorinated cycloalkyl groups containing three to ten cyclic carbon atoms, and combinations thereof.

3. The compound according to claim 1, wherein R 3 and R 4 It's not hydrogen.

4. The compound according to claim 1, wherein R 3 and R 4 At least one of them is selected from the following groups: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

5. The compound according to claim 1, wherein the ligand L A Choose from the following groups: , , and .

6. The compound according to claim 1, wherein the ligand L A Choose from the following groups: L as defined below Ak : L Ak Based on the structure of Form IV, , where R 3 R 4 And X is defined as: And L Ak Based on the structure of formula V, , where R 3 R 4 And X is defined as: Where R B1 To R B4 It has the following structure: , , and .

7. The compound according to claim 6, wherein the compound has the formula Ir(L Ak )2(L Bj ); in k It is an integer as defined in claim 6, and j It is an integer from 1 to 17; and the ligand L is among them. B1 To L B17 The definition is as follows: , , , , , , , , , , , , , , , and .

8. A first apparatus comprising a first organic light-emitting device, the first organic light-emitting device comprising: anode; cathode; and An emitting layer disposed between the anode and the cathode, comprising the compound according to any one of claims 1-7.

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