Organic electroluminescent materials and devices

Abstract

The main application relates to organic electroluminescent materials and devices. Compounds containing a fused indole containing at least one of the following as a further structural element: pyrimidine, triazine, quinazoline, benzene, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene, pyridine, pyrazine, fluorene, dibenzofuran, dibenzothiophene, carbazole, quinoline, isoquinoline, triarylboron group or quinoxaline, which can be further substituted, are provided. Formulations comprising these compounds are also provided. OLEDs and related consumer products utilizing these compounds are further provided.

Description

[0001] This application is a divisional application of Chinese Invention Patent Application No. 202111287534.3 entitled "Organic Electroluminescent Material and Device" (filed on November 2, 2021).

[0002] This application claims priority to U.S. Provisional Application No. 63 / 108,490, filed November 2, 2020, pursuant to 35 USC § 119(e), the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to organometallic compounds and formulations and their various uses, including as a host or emitter in devices such as organic light-emitting diodes and related electronic devices. Background Technology

[0004] For various reasons, optoelectronic devices utilizing organic materials are becoming increasingly popular. Many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, make them more suitable 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.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels suited to emitting specific colors (called "saturated" colors). Specifically, these standards require pixels saturated with red, green, and blue light. 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-emitting-layer (EML) devices or stacked structures. Color can be measured using the CIE coordinate system, well-known in the field. Summary of the Invention

[0007] In one aspect, this disclosure provides a compound of formula I:

[0008] Formula I;

[0009] in

[0010] X1 -X 17 Each can be either C or N independently;

[0011] R A R B R C and R D Each can be used independently to represent monosubstituted to the maximum permissible substitution, or no substitution.

[0012] R A R B R C and R D Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boronyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl and combinations thereof;

[0013] R A R B R C and R D At least one of them is bonded to its respective ring by a single bond and comprises pyrimidine, triazine, quinazoline, benzene, biphenyl, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene oxide, pyridine, pyrazine, fluorene, dibenzofuran, dibenzothiophene, carbazole, quinoline, isoquinoline, triarylboryl or quinoxaline, which can be further substituted.

[0014] In another aspect, this disclosure provides a formulation comprising the compound according to the invention as described herein.

[0015] In another aspect, this disclosure provides an organic light-emitting device (OLED) comprising an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound according to the invention as described herein.

[0016] In another aspect, this disclosure provides a consumer product comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound according to the invention as described herein.

[0017] In another aspect, this disclosure provides a chemical structure selected from the group consisting of isomers, regioisomers, stereoisomers, monomers, polymers, macromolecules, and supramolecular molecules, wherein the chemical structure comprises a compound or a monovalent or multivalent variant thereof as described herein according to the invention. Attached Figure Description

[0018] Figure 1 An organic light-emitting device is shown.

[0019] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated. Detailed Implementation

[0020] A. Terminology

[0021] Unless otherwise specified, the following terms as used herein are defined as follows:

[0022] As used herein, the term "organic" includes both polymeric materials and 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 a 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 on 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 all dendritic polymers currently used in the OLED field are considered small molecules.

[0023] 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" "above" the second layer, the first layer is placed further away from the substrate. Unless 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" "above" the anode.

[0024] As used herein, “solution-handleable” means capable of dissolving, dispersing or transporting in and / or depositing from a liquid medium in the form of a solution or suspension.

[0025] When a ligand is considered to directly contribute to the photosensitivity of the emissive material, the ligand may be referred to as "photosensitive." When a ligand is considered not to contribute to the photosensitivity of the emissive material, the ligand may be referred to as "auxiliary," but auxiliary ligands can alter the properties of photosensitizing ligands.

[0026] As used herein, and as will generally be understood by those skilled in the art, if the 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 than" 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 an IP with a smaller absolute value (less negative IP). Similarly, a higher LUMO level corresponds to an electron affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with the vacuum level at the top, 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.

[0027] As used herein, and as will generally 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 the work function is typically measured as a negative number relative to the vacuum level, meaning that the “higher” work function is more negative. On a conventional energy level diagram with the vacuum level at the top, the “higher” work function is illustrated as being farther from the vacuum level in the downward direction. Therefore, the definitions of HOMO and LUMO levels follow different rules than those for the work function.

[0028] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0029] The term "acyl" refers to the substituted carbonyl group (C(O)-R). s ).

[0030] The term "ester" refers to the substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0031] The term "ether" refers to -OR s Group.

[0032] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0033] The term "selenium-based" refers to -SeR s Group.

[0034] The term "sulfinyl" refers to -S(O)-R s Group.

[0035] The term "sulfonyl" refers to -SO2-R s Group.

[0036] The term "phosphin" refers to -P(R) s )3 groups, wherein each R s They can be the same or different.

[0037] The term "silyl" refers to -Si(R) s )3 groups, wherein each R s They can be the same or different.

[0038] The term "germanium alkyl" refers to -Ge(R) s )3 groups, wherein each R s They can be the same or different.

[0039] The term "boron-based" refers to -B(R) s )2 group or its Lewis adduct -B(R s )3 groups, of which R s They can be the same or different.

[0040] In each of the above, R s It can be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s Choose from the following groups: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0041] The term "alkyl" refers to and includes 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.

[0042] The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 cyclic carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. Additionally, the cycloalkyl group may optionally be substituted.

[0043] The terms "heteroalkyl" or "heterocyclic alkyl" refer to alkyl or cycloalkyl groups having at least one carbon atom substituted with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocyclic alkyl group may optionally be substituted.

[0044] The term "alkenyl" refers to and includes both straight-chain and branched alkenyl groups. An alkenyl group is essentially an alkyl group comprising at least one carbon-carbon double bond in an alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising at least one carbon-carbon double bond in a cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, alkenyl, cycloalkenyl, or heteroalkenyl groups may optionally be substituted.

[0045] The term "alkynyl" refers to and includes both straight-chain and branched alkynyl groups. An alkynyl group is generally an alkyl group that includes at least one carbon-carbon triple bond in an alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may optionally be substituted.

[0046] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group that has been substituted with an aryl group. Additionally, aralkyl groups may optionally be substituted.

[0047] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably O, S, or N. Aromatic heterocyclic groups are used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic 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 / thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group may be optionally substituted.

[0048] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring 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 an aromatic hydrocarbon group; 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, β-, perylene, and azulene, with phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene being preferred. Additionally, the aryl group may optionally be substituted.

[0049] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems comprising at least one heteroatom. Heteroatoms include, but are not limited to, O, S, N, P, B, Si, and Se. In many cases, O, S, or N are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings having 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic systems may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups 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, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole-carbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazole Phosphorus, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, and selelenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazynylene, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0050] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, as well as their respective aza analogs, are of particular interest.

[0051] As used herein, the terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, ynyl, aralkyl, heterocycloyl, aryl, and heteroaryl are either unsubstituted or substituted independently by one or more general substituents.

[0052] In many cases, the substituents are generally selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, germanalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, boronyl, selenyl, and combinations thereof.

[0053] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, boronyl, and combinations thereof.

[0054] In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boronyl, aryl, heteroaryl, thio, and combinations thereof.

[0055] In other cases, the most preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0056] The terms "substituted" and "substituted" refer to substituents other than H being bonded to the relevant position, such as carbon or nitrogen. For example, when R... 1 When representing a single substitution, then an R 1 It must not be H (i.e., substitution). Similarly, when R 1 When representing disubstituted substitution, then the two Rs 1 It must not be H. Similarly, when R... 1 When R represents zero or no substitution, 1 For example, it could be hydrogen with available valences in the ring atom, such as the carbon atom in benzene and the nitrogen atom in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in a ring structure will depend on the total number of available valences in the ring atoms.

[0057] As used herein, “combination thereof” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents; and halogen, alkyl, and aryl groups can be combined to form haloaralkyl groups. In one instance, the term substitution includes a combination of two to four listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0058] The term "aza" in the passages described herein, namely aza-dibenzofuran, aza-dibenzothiophene, etc., refers to the fact that one or more of the CH groups in the corresponding aromatic ring can be replaced by nitrogen atoms, for example and without any limitation. Azatribenzene encompasses dibenzo[ f,h Quinoxaline and dibenzo[ f,h Quinoline. Other nitrogen analogs of the aza-derived compounds described above will be readily apparent to those skilled in the art, and all such analogs are intended to be covered by the terminology set forth herein.

[0059] As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US 2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angewandte Chemie International Edition (Review) 2007, 46, 7744-65 (which are incorporated herein by reference in their entirety) describe efficient pathways for the deuteration of methylene hydrogen in benzylamine and the replacement of aromatic cyclic hydrogens with deuterium.

[0060] It should be understood that when a molecular fragment is described as a substituent or additionally linked 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 linked fragments are considered equivalent.

[0061] In some cases, a pair of adjacent substituents may optionally join or fuse into a ring. Preferred rings are five-, six-, or seven-membered carbon rings or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved may be adjacent to each other on the same ring, or on two neighboring rings having two closest available substituted positions (such as the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene), provided that a stable fused ring system can be formed.

[0062] B. Compounds disclosed herein

[0063] In one aspect, this disclosure provides a compound of formula I:

[0064] Formula I;

[0065] in

[0066] X 1 -X 17 Each can be either C or N independently;

[0067] R A R B R C and R D Each can be used independently to represent monosubstituted to the maximum permissible substitution, or no substitution.

[0068] R A R B R C and R D Each is independently hydrogen or a substituent selected from the general list of substituents disclosed above;

[0069] R A R B R C and R D At least one of them is bonded to its respective ring by a single bond and comprises pyrimidine, triazine, quinazoline, benzene, biphenyl, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene oxide, pyridine, pyrazine, fluorene, dibenzofuran, dibenzothiophene, carbazole, quinoline, isoquinoline, triarylboryl or quinoxaline, which can be further substituted.

[0070] In one embodiment, R A R B R C and R D Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

[0071] In one embodiment, R in equation I above A R B R C and R D One or two of them contain pyrimidine, triazine, quinazoline, carbazole, benzene, biphenyl, naphthalene, or triphenyl.

[0072] Further embodiments relate to the meaning of X in Formula I: In one embodiment, the maximum number of nitrogen atoms that can be connected to each other within the ring is two. According to further embodiments, one or both of the following hold: X 1 -X 17 Only one of them is N; X 1 -X 4 At least one of them is N; X 5 -X 9 At least one of them is N; X 10 -X 13 At least one of them is N; or X 14 -X 17 At least one of them is N.

[0073] In another embodiment, R A R B R C and R D At least one of the choices R is as follows: A1 To R A16 Any group consisting of any one of the following:

[0074] R A1 , R A2 , R A3 , R A4 , R A5 , R A6 , R A7 , R A8 , R A9 , R A10 , R A11 , R A12 , R A13 , R A14 , R A15 and R A16 ;

[0075] Where R' and R'' are independently hydrogen or substituents selected from the group consisting of: aryl, phenyl, biphenyl, naphthyl, carbazolyl, triazinyl, pyrimidinyl, quinazolinyl, and triphenylene; X 18 -X 22 It is C or N; and Z represents NR'', O or S, where R'' is aryl or heteroaryl. Specifically, R A R B R C and R D At least one of the following groups can be freely selected:

[0076] R 1 , R 2 , R 3 ,

[0077] R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R25 、 R 26 、 R 27 、 R 28 、 R 29 、 R 30 、 R 31 、 R 32 、 R 33 、 R 34 、 R 35 、 R 36 、 R 37 、 R 38 、 R 39 、 R 40 、

[0078] R 41 、 R 42 、

[0079] R 43 、 R 44 、 R 45 、 R 46 、 R 47 、 R 48 、 R 49 、 R 50 、 R 51 、 R 52 、 R 53 、 R 54 、 R 55 、 R 56 、 R 57 、 R 58 、 R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 and R 71 .

[0080] According to a further embodiment of the present invention, the compound may be selected from the group consisting of:

[0081] , , , , , , , , , , and .

[0082] Specifically, the compounds can be selected from the following group:

[0083]

[0084]

[0085] , , , , , ,

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , and .

[0100] C. OLEDs and devices disclosed herein

[0101] In another aspect, this disclosure also provides an OLED device comprising a first organic layer containing compounds as disclosed in the above compound portion of this disclosure.

[0102] In some embodiments, the first organic layer may comprise compounds as disclosed in the compound portion of this disclosure above.

[0103] In some embodiments, the compound may be the host, and the first organic layer may be an emitting layer containing a phosphorescent emitter.

[0104] In some embodiments, the phosphorescent emitter may be a transition metal complex having at least one ligand or a portion of said ligand, provided that said ligand is more than a bidentate ligand selected from the group consisting of:

[0105] , , , ,

[0106] , , , , , , , , , , , , , , , , , and ,

[0107] in:

[0108] T is chosen from the group consisting of B, Al, Ga, and In;

[0109] Y 1 To Y 13 Each of them is independently selected from a group composed of carbon and nitrogen;

[0110] Y'choose freelyBR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f Groups formed;

[0111] R e and R f Capable of fusion or bonding to form rings;

[0112] R a R b R c and R d Each can independently represent zero substitution, mono substitution, or at most the maximum allowed number of substitutions for its associated ring;

[0113] R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, boronyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof; and

[0114] And R a R b R c R d R e and R f Any two adjacent substituents can fuse or join to form a ring or a polydentate ligand.

[0115] In some embodiments, the compound may be a receptor, and the OLED may further comprise a sensitizer selected from the group consisting of delayed fluorescent emitters, phosphorescent emitters, and combinations thereof.

[0116] In some embodiments, the compound may be a fluorescent emitter, a delayed fluorescent emitter, or a component of an excited-state complex of a fluorescent emitter or a delayed fluorescent emitter.

[0117] In another aspect, the OLED of this disclosure may also include an emission region containing compounds as disclosed in the above compound portion of this disclosure.

[0118] In some embodiments, the emission region may comprise a compound of formula I:

[0119] Formula I;

[0120] in

[0121] X 1 -X 17 Each can be either C or N independently;

[0122] R A R B R C and R D Each can be used independently to represent monosubstituted to the maximum permissible substitution, or no substitution.

[0123] R A R B R C and R D Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boronyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl and combinations thereof;

[0124] R A R B R C and R D At least one of them is bonded to its respective ring by a single bond and comprises pyrimidine, triazine, quinazoline, benzene, biphenyl, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene oxide, pyridine, pyrazine, fluorene, dibenzofuran, dibenzothiophene, carbazole, quinoline, isoquinoline, triarylboryl or quinoxaline, which can be further substituted.

[0125] In some embodiments, at least one of an anode, cathode, or new layer disposed on the organic emitting layer serves as a reinforcement layer. The reinforcement layer comprises a plasma material exhibiting surface plasmon resonance, which is nonradiatively coupled to the emitter material and transfers excited-state energy from the emitter material to the nonradiative mode of the surface plasmon polaritons. The reinforcement layer is provided at a threshold distance not exceeding that of the organic emitting layer, wherein, due to the presence of the reinforcement layer, the emitter material has a total nonradiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the distance at which the total nonradiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an excoupling layer. In some embodiments, the excoupling layer is disposed on the reinforcement layer on the opposite side of the organic emitting layer. In some embodiments, the excoupling layer is disposed on the side of the emitting layer opposite to the reinforcement layer, but still allows energy to be decoupled from the surface plasmon modes of the reinforcement layer. The excoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space in the form of photons. In other embodiments, the energy is scattered from the surface plasmon modes to other modes of the device, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If energy is scattered into the non-free space mode of the OLED, other decoupling schemes can be incorporated to extract the energy into free space. In some embodiments, one or more interposers may be disposed between the reinforcement layer and the decoupling layer. Examples of interposers may be dielectric materials, including organic, inorganic, perovskite, and oxide materials, and may include stacks and / or mixtures of these materials.

[0126] The enhancement layer modifies the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, modification of emission profile, changes in emission intensity and angle, changes in the stability of the emitter material, changes in OLED efficiency, and reduced efficiency roll-off of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides produces an OLED device utilizing any of the effects mentioned above. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLED according to the present invention may also include any of the other functional layers commonly found in OLEDs.

[0127] The reinforcing layer can be composed of plasma materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasma material is a material whose real portion of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasma material comprises at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys, or mixtures of these materials, as well as stacks of these materials. Generally, metamaterials are media composed of different materials, wherein the medium as a whole acts differently from the sum of its constituent material components. Specifically, we define an optically active metamaterial as a material having both a negative dielectric constant and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium whose dielectric constant or permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the medium must be uniform along the length scale of the light wavelength in the direction of propagation. Using terminology understandable to those skilled in the art, the dielectric constant of a metamaterial in the direction of propagation can be approximated by an effective medium. Plasma materials and metamaterials offer methods for controlling light propagation that can enhance OLED performance in a variety of ways.

[0128] In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has periodic, quasi-periodic, or randomly arranged wavelength-sized features, or periodic, quasi-periodic, or randomly arranged subwavelength-sized features. In some embodiments, the wavelength-sized features and subwavelength-sized features have sharp edges.

[0129] In some embodiments, the decoupling layer has periodic, quasi-periodic, or randomly arranged wavelength-sized characteristics, or periodic, quasi-periodic, or randomly arranged subwavelength-sized characteristics. In some embodiments, the decoupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the decoupling layer is composed of a plurality of nanoparticles disposed on a material. In these embodiments, decoupling can be tuned by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and / or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layering of one or more materials and / or a core of one type of material coated with a shell of a different type of material. In some embodiments, the decoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles may have an additional layer disposed thereon. In some embodiments, the polarization of emission can be tuned using the decoupling layer. Changing the dimension and periodicity of the decoupling layer can select a class of polarizations that preferentially decouple to air. In some embodiments, the decoupling layer also functions as an electrode of the device.

[0130] In another aspect, this disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise compounds as disclosed in the above compound section of this disclosure.

[0131] In some embodiments, a consumer product includes an organic light-emitting device (OLED) having an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer may contain a compound of formula I as described herein.

[0132] In some embodiments, a consumer product may be one of the following: a flat panel display, a computer monitor, a medical monitor, a television set, a signboard, a light for internal or external lighting and / or signaling, a head-up display, a fully transparent or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay with a diagonal of less than 2 inches, a 3D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a phototherapy device, and a sign.

[0133] Generally, an OLED comprises at least one organic layer disposed between and electrically connected to both the anode and cathode. When a current is applied, holes are injected into the anode and electrons into the organic layer from the cathode. The injected holes and electrons migrate toward their respective oppositely charged electrodes. When electrons and holes are localized on 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 photoemission mechanism, light is emitted. In some cases, excitons may be localized on excimers or excited-state complexes. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0134] Certain 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.

[0135] 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 within timeframes of less than 10 nanoseconds.

[0136] 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, 151-154, 1998 (“Baldo-I”); and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Applied Physics Letters, Vol. 75, 3, 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.

[0137] 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 layers. The properties and functions of these various layers, as well as example materials, are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0138] Further examples of each of these layers are available. 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 in a 50:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of emitting 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 in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes, comprising composite cathodes having a thin layer of metal (e.g., Mg:Ag) having an overlying transparent, conductive, sputtered ITO layer, are disclosed in their entirety in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. Theories and uses 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 incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. Descriptions of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0139] 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 these layers. Because the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed below 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 Provide an example of how some layers can be omitted from the structure of device 100.

[0140] Figure 1 and 2The simple layered structures described herein are provided by way of non-limiting examples, and it should be understood that embodiments of this disclosure can be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. Functional OLEDs can be obtained by combining the various layers described in different ways, or the layers can be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it should be understood that combinations of materials, such as mixtures of host and dopant, or more generally, mixtures, can 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 can 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 the different organic materials mentioned above.

[0141] 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. By another example, OLEDs with a single organic layer can be used. OLEDs can be stacked, for example as described in, for example, U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. OLED structures can deviate from... 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 described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the recessed structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0142] Unless otherwise specified, any of the layers in the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet printing (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) (as described in U.S. Patent No. 6,337,102 by Forrest et al., which are incorporated herein by reference in their entirety), and deposition by organic vapor jet printing (OVJP) (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 patterning via mask deposition, cold soldering (as described in U.S. Patents 6,294,398 and 6,468,819, which are incorporated herein by reference in their entirety), and some of the methods associated with deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit a particular deposition method. For example, branched or unbranched substituents, preferably containing at least three carbons, such as alkyl and aryl groups, 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 handleability than materials with symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the solution handling ability of small molecules.

[0143] The device manufactured according to embodiments of this disclosure 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 an environment including moisture, vapor, 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 a variety of known chemical vapor deposition techniques and may comprise compositions having a single phase and compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may contain 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 process to be considered a "mixture," the aforementioned polymeric and non-polymeric materials constituting the barrier layer should be deposited and / or deposited simultaneously under the same reaction conditions. The weight ratio of polymeric to non-polymeric materials 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.

[0144] The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of electronic component modules (or units), which can be incorporated into a variety of 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. The electronic component module may optionally include driving electronics and / or a power supply. The apparatus manufactured according to embodiments of this disclosure can be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. A consumer product incorporating an OLED is disclosed, wherein the OLED includes compounds of this disclosure in its organic layer. The consumer product should include any type of product containing one or more light sources and / or one or more of some type of visual display. Examples of the consumer products described include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablet computers, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple tiled displays, theater or stadium screens, phototherapy devices, and signage. Various control mechanisms, including passive and active matrices, can be used to control the devices manufactured according to this disclosure. Many of the devices are intended for use in temperature ranges comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0145] 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.

[0146] 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 utilize the materials and structures described herein. More generally, organic devices such as organic transistors can utilize the materials and structures described herein.

[0147] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer including carbon nanotubes.

[0148] In some embodiments, the OLED further comprises a layer including a delayed phosphor emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white pixel arrangement with a color filter. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel with a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel with a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0149] In some embodiments, the compound may be an emission dopant. In some embodiments, the compound may generate emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (TADF, also known as E-type delayed fluorescence, see, for example, U.S. Application No. 15 / 700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or a combination of these processes. In some embodiments, the emission dopant may be a racemic mixture or may be enriched with one enantiomer. In some embodiments, the compound may be homogeneous (each ligand is identical). In some embodiments, the compound may be mixed (at least one ligand is different from the others). In some embodiments, when more than one ligand coordinated to a metal is present, the ligands may all be identical. In some other embodiments, at least one ligand is different from the others. In some embodiments, each ligand may be different from each other. This also applies in embodiments where a ligand coordinated to a metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligand. Therefore, in the case where the coordinating ligands are linked together, in some embodiments all the ligands may be the same, and in some other embodiments at least one of the linking ligands may be different from (multiple) other ligands.

[0150] In some embodiments, the compound may be used as a component of an excited-state complex intended to be used as a sensitizer.

[0151] In some embodiments, the sensitizer is a single component, or one of the components, that forms the excited-state complex.

[0152] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0153] The OLEDs disclosed herein can be incorporated into one or more consumer products, electronic component modules, and lighting panels. The organic layer can be an emission layer, and the compound can be an emission dopant in some embodiments, while in other embodiments it can be a non-emission dopant.

[0154] In another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components selected from the group consisting of: solvents, a host, hole injection materials, hole transport materials, electron blocking materials, hole blocking materials, and electron transport materials.

[0155] This disclosure covers any chemical structure comprising the novel compounds of this disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but in which one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but in which more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecular compounds, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

[0156] D. Combinations of the compounds disclosed herein with other materials

[0157] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a wide variety of other materials present in the device. For example, the emission dopants disclosed herein can be used in combination with a wide variety of possible host layers, transport layers, barrier layers, injection layers, electrodes, and other 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.

[0158] a) Conductive dopants:

[0159] Charge transport layers can be doped with conductive dopants to substantially alter their charge carrier density, which in turn changes their 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, while n-type conductive dopants are used in electron transport layers.

[0160] Non-limiting examples of conductive dopants that can be used in conjunction with the materials disclosed herein in OLEDs are illustrated in the following references: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.

[0161] , , ,

[0162] , ,

[0163] , , , ,

[0164] , , and .

[0165] b) HIL / HTL:

[0166] The hole injection / transport materials used in this disclosure are not particularly limited, and any compound may be used, provided that the compound is commonly used as a hole injection / transport material. Examples of 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 semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylhexacarbonitrile; metal complexes; and crosslinkable compounds.

[0167] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures:

[0168] , , , and .

[0169] Ar 1 To Ar 9 Each of these is selected from the following groups: the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, phenylene oxide, perylene, and azurite; the group consisting of, for example, 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, indazole, inoxazine Benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, xanthracene, 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 cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and bonded 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, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0170] In one aspect, Ar 1 To Ar 9 Choose independently from the following groups:

[0171]

[0172] 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 It has the same functional groups as defined above.

[0173] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0174]

[0175] Met is a metal with 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 bound to the metal; and k'+k" is the maximum number of ligands that can be bound to the metal.

[0176] In one aspect, (Y) 101 -Y 102 (Y) is a 2-phenylpyridine derivative. In another aspect, (Y) 101 -Y 102 Met is a carbapenem ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In yet another aspect, the metal complex possesses properties compared to Fc. + The minimum oxidation potential in solution with / Fc coupling is less than about 0.6 V.

[0177] Non-limiting examples of HIL and HTL materials in OLEDs that can be used in combination with the materials disclosed herein are illustrated below, along with references to those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791、WO2014104514、WO2014157018。、

[0178] 、 、

[0179] 、 、

[0180] 、 、

[0181] 、 、

[0182] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ,

[0183] and .

[0184] c) EBL:

[0185] 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 generally 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.

[0186] d) Main body:

[0187] The light-emitting layer of the organic EL device disclosed herein 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 may be used, as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material can be used with any dopant, as long as the triplet criterion is satisfied.

[0188] Examples of metal complexes used as the host preferably have the following general formula:

[0189]

[0190] 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 101 It is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be bound to the metal; and k' + k" is the maximum number of ligands that can be bound to the metal.

[0191] In one respect, metal complexes are:

[0192]

[0193] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0194] In the other case, Met is selected from Ir and Pt. In the other case, (Y 103 -Y 104 ) is a carbaene ligand.

[0195] In one aspect, the host compound contains at least one selected from the group consisting of, for example, aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, β-carbamate, perylene, and azurite; and 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, benzene Imidazole, indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, cycloline, quinazoline, quinoxaline, naphthidine, phthalazine, pteridine, xanthracene, 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 cyclic structural units being groups of the same or different types selected from aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups and 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 option in each group may be unsubstituted or may be substituted by substituents selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphin, and combinations thereof.

[0196] In one aspect, the host compound contains at least one of the following groups in its molecule:

[0197] , , , , ,

[0198] , , , , , , ,

[0199] , , ,

[0200] , , and ,

[0201] Where R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, and when it is aryl or heteroaryl, it has a definition similar to that of Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 Independently selected from C (including CH) or N. Z 101 and Z 102 Independently selected from NR 101 、O or S.

[0202] Non-limiting examples of material combinations disclosed herein used as host materials in OLEDs are illustrated below, along with references to those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2009 0017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, U S20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO200 6114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0203] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0204] e) Other emitters:

[0205] One or more other emitter dopants may be used in conjunction with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used, as long as the compound is commonly 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.

[0206] Non-limiting examples of emitter materials in 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, KR201200 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, 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。、

[0207] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0208] f)HBL:

[0209] Hole blocking layers (HBLs) can be used to reduce the number of holes and / or excitons leaving the emitter layer. The presence of such blocking layers in a device can result in generally higher efficiency and / or longer lifetime compared to similar devices lacking a blocking layer. Furthermore, blocking layers 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.

[0210] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as those used in the subject described above.

[0211] In another aspect, the compounds used in HBL contain at least one of the following groups in their molecules:

[0212]

[0213] Where k is an integer from 1 to 20; L101 It is another ligand, and k' is an integer from 1 to 3.

[0214] g)ETL:

[0215] An electron transport layer (ETL) may comprise a material capable of transporting electrons. The ETL may 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 may be used, provided it is typically used for electron transport.

[0216] In one aspect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0217]

[0218]

[0219] Where R 101 The group consisting of the following is selected: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof, which, when aryl or heteroaryl, have a similar definition to Ar as described above. 1 To Ar 3 It has a similar definition to Ar mentioned above. k is an integer from 1 to 20. X 101 To X 108 Selected from C (including CH) or N.

[0220] In another aspect, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0221]

[0222] Wherein (ON) or (NN) are bidentate ligands of metals 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 the metal.

[0223] Non-limiting examples of ETL materials that can be used in OLEDs 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,

[0224] , , ,

[0225] , , ,

[0226] , , , , , , , , , , , , , , , , , , , , , ,

[0227] , , ,

[0228] , and .

[0229] h) Charge Generation Layer (CGL)

[0230] 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.

[0231] In any of the compounds mentioned above used in each layer of an OLED device, hydrogen atoms can be partially or fully deuterated. Therefore, any specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., can be in their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0232] 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 substituted with other materials and structures without departing from the spirit of the invention. The claimed invention 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.

[0233] Example

[0234] (I) Synthesis Examples

[0235] Synthesis 11-( 9H -Carbazole-9-yl)-14-phenylindolo[1,2-f]phenanthridine

[0236] Step 1. Synthesis of 11-chloroindolo[1,2-f]phenanthridine

[0237]

[0238] 6-Chloro-1H-indole-2-carboxylic acid (4.57 g, 23.36 mmol), dibenzo[b,d]indole-5-onium trifluoromethanesulfonate (15.01 g, 35.0 mmol), diacetoxypalladium (0.525 g, 2.336 mmol), ethoxydiphenylphosphine (1.076 g, 4.67 mmol), and DMF (140 mL) were added to a 500 mL flask under air. The mixture was bubbled with nitrogen and maintained under nitrogen atmosphere. Potassium carbonate (7.10 g, 51.4 mmol) was then added, and the flask was placed in an oil bath preheated to 145 °C. After 22 hours, the reaction mixture was cooled to room temperature and diluted with 500 mL of DCM. The solution was mixed with water (1 L). A heavy emulsion appeared and was disrupted by the slow addition of solid LiCl (100 g). The organic layer was separated, and the aqueous layer was further extracted with DCM (2 × 500 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated. The residue was dissolved in DCM and adsorbed onto diatomaceous earth. The powder was eluted on silica gel by vacuum chromatography with DCM / heptane (0-10%). The eluates containing the purified product were combined by TLC analysis and concentrated to give 11-chloroindolo[1,2-f]phenanthridine (2.57 g, 36% yield) as a yellow solid.

[0239] Step 2. Synthesis of 14-bromo-11-chloroindolo[1,2-f]phenanthridine

[0240]

[0241] 11-Chloroindolo[1,2-f]phenanthridine (0.761 g, 2.52 mmol) and THF (39.5 mL) were added to 250 mL of RB. The solution was stirred at 13 °C. 1-Bromopyrrolidine-2,5-dione (0.449 g, 2.52 mmol) in THF (11.85 mL) was added to the stirred solution. The mixture was stirred for 2.5 h. The solution was then heated and 40 mL of THF was added, and the mixture was heated again until all the contents were dissolved and the solution was clear. The THF solution was then poured into stirred methanol (1 L) and stirred for 3.5 h, after which the solid was filtered off. The solid was dried in a vacuum oven to give 0.807 g (84% yield) of product.

[0242] Step 3. Synthesis of 11-chloro-14-phenylindolo[1,2-f]phenanthridine

[0243]

[0244] Under nitrogen atmosphere, 14-bromo-11-chloroindolo[1,2-f]phenanthreneidine (1 g, 2.63 mmol), phenylboronic acid (0.384 g, 3.15 mmol), potassium carbonate (0.908 g, 6.57 mmol), THF (42.0 mL), and water (10.51 mL) were added to a 100 mL three-necked flask. The reaction mixture was heated to reflux and maintained for 24 hours. After cooling to room temperature, the solution was filtered through a short silica stopper, and the organic matter passing through the stopper was washed with DCM. The filtrate was concentrated, and the resulting solid was dried under reduced pressure. The semi-crude substance was used without further purification, assuming a quantitative yield.

[0245] Step 4. Synthesis of 11-(9H-carbazol-9-yl)-14-phenylindolo[1,2-f]phenanthridine

[0246]

[0247] 11-Chloro-14-phenylindolo[1,2-f]phenanthreneidine (1.163 g, 3.08 mmol) and sodium 2-methylprop-2-ol (0.583 g, 6.07 mmol) were added to a dry 0.1 L 3-necked flask equipped with a water condenser, magnetic stirrer, and thermocouple sheath under nitrogen atmosphere, and the mixture was degassed with a constant stream of nitrogen. Dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (0.172 g, 0.419 mmol) and Pd2dba3 (0.172 g, 0.188 mmol) were added, followed by toluene (25.6 ml), and the resulting mixture was further degassed with a continuous stream of N2. The reaction mixture was heated to reflux. The reaction mixture was filtered through a stopper containing silica gel and basic alumina and eluted with hot toluene, providing 1.3 g of the desired product (83% yield). The product was further processed. The substance was dissolved in approximately 60 mL of DCM under heating and then slowly poured into 100 mL of methanol. The resulting solid was collected by suction filtration. The solid was mixed with product from another batch to give 1.8 g of product, which was dissolved in 100 mL of DCM under heating and then poured into 100 mL of methanol, followed by filtration. The resulting solid was then dissolved in 200 mL of DCM and slowly poured into 500 mL of methanol. The solid was collected by suction filtration to give 1.08 g of 11-(9H-carbazole-9-yl)-14-phenylindolo[1,2-f]phenanthridine as a yellow solid.

[0248] (II) Device Examples

[0249] All example devices were subjected to high vacuum (<10) -7The device was manufactured by thermal evaporation. The anode electrode was 1,150 Å indium tin oxide (ITO). The cathode consisted of 10 Å Liq (lithium 8-hydroxyquinoline) followed by 1,000 Å Al. All devices were immediately sealed in a nitrogen glove box (<1 ppm H2O and O2) with an epoxy-sealed glass cap, incorporating a desiccant into the packaging. The organic stack of the device example consisted sequentially from the ITO surface as follows: 100 Å HAT-CN as a hole injection layer (HIL); 450 Å HTM as a hole transport layer (HTL); and a 400 Å thick emitter layer (EML). The emitter layer contained a red host H1 (the compound of this invention) and 3 wt% red emitter RD1. Following the EML was 350 Å of Liq (lithium 8-hydroxyquinoline) doped with 40% ETM as an electron transport layer (ETL). The device structure is shown in Table 1.

[0250] The chemical structure of the materials used in the device is shown below.

[0251]

[0252]

[0253] After manufacturing, the device's EL and JVL performance were measured. Device Example 1 emits red light with a maximum wavelength of 625 nm, defined by the red emitter RD1. The device performance is shown in Table 2.

[0254] Table 1. Device Instance Layer Structure

[0255]

[0256] Table 2. Device performance of Example 1

[0257]

[0258] Based on the device data in Table 2, it is shown that the compound H1 of the present invention acts as a red phosphorescent host material and has reasonable performance.

Claims

1. A compound of formula I, Equation I; in X 1 -X 17 Each can be either C or N independently; R A R B R C and R D Each can be used independently to represent monosubstituted to the maximum permissible substitution, or no substitution. R A R B R C and R D Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boronyl, germanyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof; R A R B R C and R D At least one of them is bonded to its respective ring by a single bond and comprises pyrimidine, triazine, quinazoline, benzene, biphenyl, biphenyl, terphenyl, naphthalene, phenanthrene, anthracene, triphenylene oxide, pyridine, pyrazine, fluorene, dibenzofuran, dibenzothiophene, carbazole, quinoline, isoquinoline, triarylboryl or quinoxaline, which may be further substituted.

2. The compound according to claim 1, wherein R A R B R C and R D Each of them is independently hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof.

3. The compound according to claim 1, wherein R A R B R C and R D One or two of them contain pyrimidine, triazine, quinazoline, carbazole, benzene, biphenyl, naphthalene, or triphenyl.

4. The compound according to claim 1, wherein X 1 -X 17 It is C, or X among them. 1 -X 17 Only one of them is N.

5. The compound according to claim 1, wherein X 1 -X 4 At least one of them is N, and / or where X is 5 -X 9 At least one of them is N, and / or where X is 10 -X 13 At least one of them is N, and / or where X is 14 -X 17 At least one of them is N.

6. The compound according to claim 1, wherein R A R B R C and R D At least one of the choices R is as follows: A1 To R A16 Any group consisting of any one of the following: R A1 、 R A2 、 R A3 、 R A4 、 R A5 、 R A6 、 R A7 、 R A8 、 R A9 、 R A10 、 R A11 、 R A12 、 R A13 、 R A14 、 R A15 and R A16 ; in R' and R'' are independently hydrogen or substituents selected from the group consisting of: aryl, phenyl, biphenyl, naphthyl, carbazolyl, triazinyl, pyrimidinyl, quinazolinyl, and triphenylene; X 18 -X 22 It is C or N; and Z represents NR'', O, or S, where R'' is aryl or heteroaryl.

7. The compound according to claim 1, wherein R A R B R C and R D At least one of them is selected from the following groups: R 1 、 R 2 、 R 3 、 R 4 、 R 5 、 R 6 、 R 7 、 R 8 、 R 9 、 R 10 、 R 11 、 R 12 、 R 13 、 R 14 、 R 15 、 R 16 、 R 17 、 R 18 、 R 19 、 R 20 、 R 21 、 R 22 、 R 23 、 R 24 、 R 25 、 R 26 、 R 27 、 R 28 、 R 29 、 R 30 、 R 31 、 R 32 、 R 33 、 R 34 、 R 35 、 R 36 、 R 37 、 R 38 、 R 39 、 R 40 、 R 41 、 R 42 、 R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 and R 71 .

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

9. The compound of claim 1, wherein the compound is selected from the group consisting of: 、 、 、 、 、 、 . , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

10. An organic light-emitting device (OLED) comprising: anode; cathode; and An organic layer disposed between the anode and the cathode, wherein the organic layer is an emission layer and the compound is an emission dopant or a non-emission dopant. The organic layer comprises the compound according to claim 1, wherein the compound is the host, and the organic layer is an emitting layer comprising a phosphorescent emitter.

11. The OLED of claim 10, wherein the phosphorescent emitter is a transition metal complex having at least one ligand or a portion of said ligand, provided that said ligand is more than a bidentate ligand selected from the group consisting of: , , , , , , , , , , , , , , , , , , , , , and , in: T is chosen from the group consisting of B, Al, Ga, and In; Y 1 To Y 13 Each of them is independently selected from a group composed of carbon and nitrogen; Y'choose freelyBR e NR e PR e ,O,S,Se,C=O,S=O,SO2,CR e R f SiR e R f and GeR e R f Groups formed; R e and R f Capable of fusion or bonding to form rings; R a R b R c and R d Each can independently represent zero substitution, mono substitution, or at most the maximum allowed number of substitutions for its associated ring; R a1 R b1 R c1 R d1 R a R b R c R d R e and R f Each of these groups is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogroup, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, boronyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, selenyl, and combinations thereof; and And R a R b R c R d R e and R f Any two adjacent substituents can fuse or join to form a ring or a polydentate ligand.

12. The OLED of claim 10, wherein the compound is a receptor, and the OLED further comprises a sensitizer selected from the group consisting of delayed fluorescent emitters, phosphorescent emitters, and combinations thereof.

13. The OLED of claim 10, wherein the compound is a fluorescent emitter, a delayed fluorescent emitter, or a component of an excited-state complex of a fluorescent emitter or a delayed fluorescent emitter.

14. A consumer product comprising an organic light-emitting device (OLED), said organic light-emitting device comprising: anode; cathode; and An organic layer disposed between the anode and the cathode. The organic layer therein comprises the compound according to claim 1.

15. A metal complex having the following formula: Where (NN) is a bidentate ligand of a metal that coordinates with atoms N and N-coordinate atoms; 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.

Images