Organic electroluminescent materials and devices

Abstract

This application relates to organic electroluminescent materials and devices. Organic metal compounds are provided. Formulations comprising these organic metal compounds are also provided. OLEDs and related consumer products utilizing the disclosed compounds and Pt complex compounds are additionally provided.

Description

[0001] This application is a divisional application of the invention patent application filed on April 1, 2021, with application number 202110354370.5 and invention title "Organic Electroluminescent Materials and Devices". Cross-reference of related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 036,764, filed June 9, 2020, pursuant to 35 USC § 119(e), the entire contents of which are incorporated herein by reference. This application is also a partial continuation to U.S. Patent Application No. 16 / 841,182, filed April 6, 2020, which claims priority to 35 USC § 120, which is a partial continuation to U.S. Application No. 16 / 683,507, filed November 14, 2019, which in turn claims priority to U.S. Provisional Application No. 62 / 772,403, filed November 28, 2018. All of these confirmed applications are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure generally relates to organometallic compounds and formulations and their various uses, including as emitters 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 group of compounds and formulations thereof as described herein.

[0008] In another aspect, this disclosure provides an OLED having an emission layer comprising a first host compound of formula I, a second host compound containing a biscarbazole linker, and a Pt complex as described herein.

[0009] In another aspect, this disclosure provides a consumer product comprising an OLED having an emitting layer comprising a first host compound of formula I, a second host compound having a biscarbazole linker, and a Pt complex as described herein. Attached Figure Description

[0011] Figure 1 An organic light-emitting device is shown.

[0012] Figure 2 An inverted organic light-emitting device without an independent electron transport layer is demonstrated.

[0013] Figure 3 The normalized phosphorescence emission spectra of the two compounds disclosed in this disclosure are shown. Detailed Implementation

[0014] A. Terminology

[0015] Unless otherwise specified, the following terms as used herein are defined as follows:

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] The terms “halogen,” “halogen,” and “halogen group” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0023] The term "acyl" refers to the substituted carbonyl group (C(O)-R). s ).

[0024] The term "ester" refers to the substituted oxycarbonyl group (-OC(O)-R). s or -C(O)-OR s ) group.

[0025] The term "ether" refers to -OR s Group.

[0026] The terms "thio-" or "thioether" are used interchangeably and refer to -SR s Group.

[0027] The term "sulfinyl" refers to -S(O)-R s Group.

[0028] The term "sulfonyl" refers to -SO2-R s Group.

[0029] The term "phosphin" refers to -P(R) s )3 groups, wherein each R s They can be the same or different.

[0030] The term "silyl" refers to -Si(R) s )3 groups, wherein each R s They can be the same or different.

[0031] The term "oxoboroyl" 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] The term "alkynyl" refers to and includes both straight-chain and branched alkynyl groups. An alkynyl group is essentially an alkyl group comprising 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] In many cases, the substituents are generally selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof.

[0045] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0046] In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, aryl, heteroaryl, thio, and combinations thereof.

[0047] In other cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] B. Compounds disclosed herein

[0055] Compounds suitable for use as host materials in OLEDs are disclosed. The disclosed host compositions comprise silane-substituted azabenzenes with two amine substitutions. The electron-deficient azabenzenes provide a good portion for electron transport. The amino group (e.g., carbazole or benzo[d]benzo[4,5]imidazo[1,2-a]imidazolium (bimbim)) provides hole transport capability while providing steric protection against aza-nitrogens. The triarylsilane substitution provides a spatially large three-dimensional structure, which improves the morphology of the emitter layer and prevents emission quenching, but breaks the aggregation of the host molecules. The high triplet energy of these hosts makes them ideal for use as hosts in blue OLEDs. Specifically, the substitution of bimbim on triazine provides a large aromatic plane for efficient hole transport while maintaining a high T1 energy.

[0056] This invention also discloses an emitter layer composition comprising the aforementioned silane-based host material and a phosphorescent planar quadrilateral platinum complex. The silane-substituted aziridine host, when used in combination with the platinum complex, has shown good device performance. The deep LUMO level of the electron-deficient aziridine host exhibits optimal performance when paired with the deep HOMO level of the platinum complex, while minimizing the formation of the excited complex.

[0057] In one aspect, this disclosure provides compounds selected from the group consisting of:

[0058] , ,

[0059] , ,

[0060] , and ,

[0061] X 1 -X 40 Each is independently C or N; R6 -R 12 Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and R 6 R 7 R 8 R 9 R 10 R 11 and R 12 Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein.

[0062] In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 At least one of them may be an aryl or heteroaryl group comprising at least three fused or unfused 6-membered aromatic rings. In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 At least one of them can be an aryl or heteroaryl group comprising at least three adjacent, non-fused 6-membered aromatic rings.

[0063] In some embodiments, for each structure, X 1 X 2 X 3 or X 4 At least one of them is N. In some embodiments, for each structure, X 1 X 2 X 3 or X 4 There is exactly one N in the set. In some embodiments, for each structure, X 1 X 2 X 3 and X 4Two of them are N. In some embodiments, for each structure, X 1 X 2 X 3 and X 4 Three of them are N. In some embodiments, for each structure, X 1 X 2 and X 4 Each is N independently.

[0064] In some embodiments, for each structure, X 5 -X 24 Each is C independently. In some embodiments, X is X for each structure. 5 -X 24 At least one of them is N. In some embodiments, X is for each structure. 5 -X 24 There is exactly one N in the set. In some embodiments, for each structure, X 25 -X 32 Each is C independently. In some embodiments, X is X for each structure. 25 -X 32 At least one of them is N. In some embodiments, for each structure, X 25 -X 32 There is exactly one N in the set. In some embodiments, for each structure, X 33 -X 40 Each is C independently. In some embodiments, X is X for each structure. 33 -X 40 At least one of them is N. In some embodiments, for each structure, X 33 -X 40 There happens to be one of them, N.

[0065] In some embodiments, the compound may be selected from the group consisting of the structures in Listing 1 below:

[0066] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and ,

[0067] Among them, each Y A Independently select groups composed of O, S, Se, and N-Ar;

[0068] Each Ar is selected from the following groups:

[0069] , , , , , , , , , , ,

[0070] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0071] In some embodiments, the compound may be selected from the group consisting of the structures listed in List 2 below:

[0072] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0073] C. OLEDs and devices disclosed herein

[0074] In another aspect, this disclosure also provides an OLED device comprising an emission layer containing: a first host compound of formula I, a second host compound comprising a biscarbazole linker, and a Pt complex as described herein.

[0075] In some embodiments, the first compound may comprise the structure of Formula I.

[0076] ,

[0077] Where X 1 -X 4 Each is independently C or N, and X 1 -X 4 At least one of them is N; where R 1 This indicates zero, single, or up to the maximum allowed number of substitutions for its connected loops; R 1 R 2 R 3 R 4 and R 5 Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein; R 1 R 2 R 3 R 4 and R 5 At least one of them contains a silyl or germanyl group; and any two adjacent R groups contain a silyl or germanyl group. 1 R 2 R 3 R 4 or R 5 They can be connected or fused to form rings; and the Pt complexes are capable of emitting light at room temperature upon photo or electrical excitation.

[0078] In some embodiments, the Pt complex has a square planar geometry. In some embodiments, the Pt complex comprises a tetradentate ligand. In some embodiments, the Pt complex comprises at least one Pt-C bond and at least one Pt-N bond. In some embodiments, the Pt complex comprises at least one Pt-carbaene bond. In some embodiments, the Pt complex is a phosphorescent emitter.

[0079] In some embodiments, the Pt complex has the structure of Formula II.

[0080] ,

[0081] In this ring, rings A, B, C, and D each independently represent a 5- or 6-membered carbon ring or heterocycle; where R... A R B R C and R DEach can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; L 1 L 2 and L 3 Each is independently selected from the following groups: direct bond, BR, BRR', NR, PR, O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", GeR'R", and their combinations; n is 0 or 1, and when n is 0, L 4 It does not exist, and when n is 1, L 4 Choose from the following groups: direct bond, BR, BRR', NR, PR, O, S, Se, C=O, S=O, SO2, CR'R", SiR'R", GeR'R", and combinations thereof; R A R B R C R D R, R', and R" are each independently hydrogen or a substituent selected from the group of universal substituents defined herein; any two adjacent R A R B R C R D R or R' can be connected to form a loop; Z 1 Z 2 Z 3 and Z 4 Each is independently C or N; and K 1 K 2 K 3 and K 4 Each of the following groups is independently selected: a direct bond, an O bond, and an S' bond, where at least two of them are direct bonds.

[0082] In some embodiments, n=0. In some embodiments, rings A, B, C, and D can all be 6-membered rings. In some embodiments, rings A, B, and C can all be 6-membered rings, and ring D can be a 5-membered ring. In some embodiments, rings A and D can be 5-membered rings, and rings B and C can be 6-membered rings. In some embodiments, K 1 K 2 K 3 and K 4 Each can be a direct key. In some embodiments, K 1 K 2 K 3 and K 4 One of them can be 0, and the rest can be direct bonds. In some embodiments, Z 1 and Z 4 It can be N, and Z 2 and Z 3 It can be C. In some embodiments, Z1 and Z 4 It can be C, and Z 2 and Z 3 It can be N. In some embodiments, L 1 L 2 and L 3 Each can be independently selected from the following groups: direct bond, NR, BR, BRR', O, S, CR'R", SiR'R", and combinations thereof. In some embodiments, L 2 It can be O. In some embodiments, L 1 and L 3 One of them can be a direct key, and the other can be an NR. In some embodiments, L 1 and L 3 All can be direct bonds. In some embodiments, the Pt complex may have at least one ligand or a portion of said ligand, provided that said ligand is more than bidentate and selected from the group consisting of:

[0083] , , , , , , , , , , , , and ,

[0084] Where Y 1 To Y 13 Each is independently selected from the group composed of carbon and nitrogen; where Y' is selected from the group composed of the following: BR 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 ;

[0085] Where R e and R f They can be fused or joined to form a ring; where R a R b R c and R d Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; where Ra R b R c R d R e and R f Each is independently hydrogen or a substituent selected from the group of universal substituents described herein; and wherein R a R b R c and R d Any two adjacent substituents can fuse or connect to form a ring or a polydentate ligand.

[0086] In some embodiments, the Pt complex may be selected from the group consisting of:

[0087] , , , , , , , , , , , , , , and ,

[0088] Where R E and R F Each can independently represent zero, a single, or up to the maximum allowed number of substitutions for its connected loops; R E R F and R N Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein; and all other variables are the same as those defined above.

[0089] In some embodiments, R A R B R C R D R E R F and R N Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. In some embodiments, R A R B R C R D R ER F and R N At least one of them may be an aryl or heteroaryl group comprising at least three fused or unfused 6-membered aromatic rings. In some embodiments, R A R B R C R D R E R F and R N At least one of them can be an aryl or heteroaryl group comprising at least three adjacent, non-fused 6-membered aromatic rings. In some embodiments, for each structure, R N It can be an aryl or heteroaryl group comprising at least three fused or unfused 6-membered aromatic rings. In some embodiments, for each structure, R N It can be an aryl or heteroaryl group containing at least three adjacent, non-fused 6-membered aromatic rings.

[0090] In some embodiments, R 1 R 2 R 3 R 4 and R 5 Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. In some embodiments, R 2 and R 3 They can be connected together to form a ring. In some embodiments, R 4 and R 5 They can be connected together to form a ring. In some embodiments, R 1 It may contain silane. In some embodiments, R 3 and R 4 At least one of them may contain a silane. In some embodiments, X 1 X 2 and X 3 Two of them can be N, and one can be C. In some embodiments, X 1 X 2 and X 3 The three in R can each be N. In some embodiments, R 1 It can be aryl or heteroaryl. In some embodiments, R 2 R 3 R 4 and R 5 Each can be aryl or heteroaryl. In some embodiments, R 2 and R 3 , or R4 and R 5 They can be linked together to form a carbazole group. In some embodiments, R 2 and R 3 , or R 4 and R 5 They can be linked together to form a 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazo group. In some embodiments, R 1 R 2 R 3 R 4 and R 5 At least one of them may contain a chemical group selected from the group consisting of: carbazole, dibenzofuran, dibenzothiophene, tetraphenylene, triazine, pyrimidine, pyridine, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium, benzo[d]benzo[4,5]imidazo[2,1-b]oxazole, benzo[d]benzo[4,5]imidazo[2,1-b]thiazole, 5H-6λ2-indolo[2,3-b]indole, 6H-benzofuran[2,3-b]indole, 6H-benzo[4,5]thieno[2,3-b]indole, and their nitrogen-containing variants.

[0091] In some embodiments, the first host compound may be selected from the group consisting of:

[0092] , , , , , , , , ,and ,

[0093] Where X 1 -X 40 Each can be either C or N independently;

[0094] Where R 6 R 7 R 8 R 9 R 10 R 11 and R 12 Each independently represents zero, a single, or up to the maximum allowed number of substitutions for its connected loops; and where R 6 R 7 R 8 R 9 R 10 R 11 and R 12Each is independently hydrogen or a substituent selected from the group of universal substituents defined herein; and any two adjacent Rs are... 6 -R 12 They can connect or fuse to form rings.

[0095] In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 At least one of them may be an aryl or heteroaryl group comprising at least three fused or unfused 6-membered aromatic rings. In some embodiments, R 6 R 7 R 8 R 9 R 10 R 11 and R 12 At least one of them can be an aryl or heteroaryl group comprising at least three adjacent, non-fused 6-membered aromatic rings.

[0096] In some embodiments, for each structure, X 1 X 2 X 3 or X 4 At least one of them is N. In some embodiments, for each structure, X 1 X 2 X 3 or X 4 There is exactly one N in the set. In some embodiments, for each structure, X 1 X 2 X 3 and X 4 Two of them are N. In some embodiments, for each structure, X 1 X 2 X 3 and X 4 Three of them are N. In some embodiments, for each structure, X 1X 2 and X 4 Each is N independently.

[0097] In some embodiments, for each structure, X 5 -X 24 Each is C independently. In some embodiments, X is X for each structure. 5 -X 24 At least one of them is N. In some embodiments, for each structure, X 5 -X 24 There is exactly one N in the set. In some embodiments, for each structure, X 25 -X 32 Each is C independently. In some embodiments, X is X for each structure. 25 -X 32 At least one of them is N. In some embodiments, for each structure, X 25 -X 32 There is exactly one N in the set. In some embodiments, for each structure, X 33 -X 40 Each is C independently. In some embodiments, X is X for each structure. 33 -X 40 At least one of them is N. In some embodiments, for each structure, X 33 -X 40 There is exactly one N in the set. In some embodiments, for each structure, X 5 -X 40 Each of them is C.

[0098] In some embodiments, the first host compound may be selected from the group consisting of the structures in List 3 below:

[0099] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

[0100] and ,

[0101] Among them, each Y A Independently select groups composed of O, S, Se, and N-Ar;

[0102] Each Ar is selected from the following groups:

[0103] , , , , , , , , , , ,

[0104] , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , and .

[0105] In some embodiments, the first host compound may be selected from the group consisting of the structures in List 4 below:

[0106] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , and .

[0107] In some embodiments, the first host compound may be selected from the group consisting of:

[0108] , , , , , , , , , , , and .

[0109] In some embodiments, the second host compound may be

[0110] or All variables are the same as those defined above.

[0111] In some embodiments, R 6 R 7 R 8 R 9 R 10 and R 11 Each can independently be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thioyl, and combinations thereof. In some embodiments, R 6 R 7 R 8 R 9 R 10 and R 11 At least one of them may be an aryl or heteroaryl group comprising at least three fused or unfused 6-membered aromatic rings. In some embodiments, R 6 R 7 R 8 R 9 R10 and R 11 At least one of them can be an aryl or heteroaryl group comprising at least three adjacent, non-fused 6-membered aromatic rings. In some embodiments, for any structure, R 10 or R 11 It can be an aryl or heteroaryl group comprising at least three fused or unfused six-membered aromatic rings. In some embodiments, for any structure, R 10 or R 11 It can be an aryl or heteroaryl group comprising at least three adjacent, non-fused 6-membered aromatic rings. In some embodiments, for any structure, R 10 or R 11 It contains the 2,2'-biphenyl moiety.

[0112] In some embodiments, for any structure, X 5 -X 12 Each is C independently. In some embodiments, for any given structure, X 13 -X 20 Each is C independently. In some embodiments, for any given structure, X 5 -X 20 Each is C independently. In some embodiments, for any given structure, X 5 -X 20 At least one of them is N. In some embodiments, for any structure, X 5 -X 20 There is exactly one N in X. In some embodiments, for any given structure, X 5 -X 12 At least one of them is N. In some embodiments, for any structure, X 5 -X 12 There is exactly one N in X. In some embodiments, for any given structure, X 13 -X 20 At least one of them is N. In some embodiments, for any structure, X 13 -X 20 There happens to be one of them, N.

[0113] In some embodiments, the second host compound may be selected from the group consisting of:

[0114] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0115] In some embodiments, the second host compound may be selected from the group consisting of:

[0116] , , , , , , , , , and .

[0117] In some embodiments, the Pt complex may be an emitter. In some embodiments, the emitter layer may comprise other compounds. In some embodiments, the other compounds may also be a co-body. In some embodiments, the co-body may comprise a chemical moiety selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, 5,9-dioxa-13b-boronana[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenene, and aza-(5,9-dioxa-13b-boronana[3,2,1-de]anthracene).

[0118] In some embodiments, the common subject can be selected from the following group:

[0119] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , and their combinations.

[0120] In another aspect, the OLED disclosed herein may also include an emission region comprising a first host compound of formula I, a second host compound comprising a biscarbazole linker, and a Pt complex as disclosed herein.

[0121] 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 preceding compound section of this disclosure.

[0122] 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 emitting layer may include: a first host compound of Formula I, a second host compound including a biscarbazole linker, and a Pt complex as described herein.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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 blocking 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 and example materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated herein by reference.

[0129] 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 luminescent 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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).

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED, wherein one or more layers in the OLED contain acceptors in the form of one or more fluorescent and / or delayed-motion fluorescent emitters. In some embodiments, the compound can be used as a component of an excited-state complex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be able to transfer energy to the acceptor and the acceptor to emit energy or further transfer energy to the final emitter. The acceptor concentration can range from 0.001% to 100%. The acceptor can be in the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, emission can be generated by any one or all of the sensitizer, the acceptor, and the final emitter.

[0142] According to another aspect, a formulation comprising the compounds described herein is also disclosed.

[0143] 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.

[0144] 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.

[0145] 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 by a bond to the remainder 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 by one or more bonds to the remainder 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.

[0146] D. Combinations of the compounds disclosed herein with other materials

[0147] The materials described herein for use in specific layers of organic light-emitting devices can be used in combination with a variety of other materials present in the device. For example, the emission dopants disclosed herein can be used in combination with a wide variety of host layers, transport layers, blocking 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.

[0148] a) Conductive dopants:

[0149] 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 creating 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.

[0150] 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.

[0151] , , ,

[0152] , ,

[0153] , , , ,

[0154] , , and .

[0155] b) HIL / HTL:

[0156] 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.

[0157] Examples of aromatic amine derivatives used for HIL or HTL include (but are not limited to) the following general structures:

[0158] , , , and .

[0159] Ar 1 To Ar 9Each of these is selected from: the group consisting of, for example, aromatic cyclic compounds such as: benzene, biphenyl, biphenylene, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, β-carbamate, perylene, and azulene; and 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, benzene The group consisting of 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 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.

[0160] In one aspect, Ar 1 To Ar 9 Choose independently from the following groups:

[0161]

[0162] 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.

[0163] Examples of metal complexes used in HIL or HTL include (but are not limited to) the following general formulas:

[0164]

[0165] Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y101 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.

[0166] 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.

[0167] 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。、

[0168] 、 、

[0169] 、 、

[0170] 、 、

[0171] 、 、

[0172] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ,

[0173] ,and .

[0174] c) EBL:

[0175] 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.

[0176] d) Main body:

[0177] 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.

[0178] Examples of metal complexes used as the host preferably have the following general formula:

[0179]

[0180] 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.

[0181] In one respect, metal complexes are:

[0182]

[0183] (ON) is a bidentate ligand of a metal that coordinates with O and N atoms.

[0184] In the other case, Met is selected from Ir and Pt. In the other case, (Y 103 -Y 104 ) is a carbaene ligand.

[0185] 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.

[0186] In one aspect, the host compound contains at least one of the following groups in its molecule:

[0187] , , , , ,

[0188] , , , , , , ,

[0189] , , , , , ,and ,

[0190] 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.

[0191] 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,

[0192] , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0193] e) Other emitters:

[0194] 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.

[0195] 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。、

[0196] 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0197] f) HBL:

[0198] 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.

[0199] 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.

[0200] In another aspect, the compounds used in HBL contain at least one of the following groups in their molecules:

[0201]

[0202] Where k is an integer from 1 to 20; L101 It is another ligand, and k' is an integer from 1 to 3.

[0203] g) ETL:

[0204] 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.

[0205] In one aspect, the compounds used in ETL contain at least one of the following groups in their molecules:

[0206]

[0207]

[0208] 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.

[0209] In another aspect, the metal complexes used in ETL contain (but are not limited to) the following general formula:

[0210]

[0211] 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.

[0212] 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,

[0213] , , ,

[0214] , , ,

[0215] , , , , , , , , , , , , , , , , , , , , , , , , ,

[0216] , and .

[0217] h) Charge Generation Layer (CGL)

[0218] 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.

[0219] 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.

[0220] 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.

[0221] E. Experimental Section

[0222] Synthesis of EH-10

[0223]

[0224] Step 1: Hexane containing 1.6 M n-butyllithium (26.5 mL, 42.4 mmol, 1.0 equivalent) was added dropwise over 20 minutes to a solution of 1,3-dibromobenzene (10.0 g, 42.4 mmol, 1.0 equivalent) in anhydrous THF (250 mL), while maintaining the temperature below -60°C. The reaction mixture was stirred at -78°C for 2 hours. Then, anhydrous THF (50 mL) containing chlorotriphenylsilane (15.0 g, 50.9 mmol, 1.2 equivalent) was added dropwise to the above solution over 10 minutes, while the reaction mixture was slowly heated to room temperature overnight. The reaction mixture was poured into water (100 mL) and extracted with ethyl acetate (300 mL). The organic layer was washed with saturated brine (100 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by gradient elution with 0 to 10% dichloromethane / hexane on a Biotage automated chromatography system (Biotage, 200 g silica column) to give (3-bromophenyl)triphenylsilane (9.33 g, 53% yield) as a pale yellow solid.

[0225] Step 2: 1.4 M sec-butyllithium (15.93 mL, 22.30 mmol, 1.1 equivalents) in cyclohexane was added dropwise over 20 minutes to a solution of (3-bromophenyl)triphenylsilane (8.42 g, 20.27 mmol, 1.0 equivalents) in THF (90 mL), while maintaining the temperature below -60 °C. The reaction mixture was stirred at -78 °C for 2.5 h (LC / MS analysis indicated bromide depletion after 1.25 h). Trimethyl borate (2.49 mL, 22.30 mmol, 1.1 equivalents) was added dropwise over 30 seconds at -78 °C, and the reaction mixture was heated to room temperature overnight. The reaction mixture was cooled to 0 °C and a saturated aqueous solution of ammonium chloride (60 mL) was added. The layers were separated, and the aqueous layer was extracted with dichloromethane (3 × 200 mL). The combined organic layers were concentrated under reduced pressure. The crude product was purified by gradient elution with 0 to 1% methanol / dichloromethane on an Interchim automated chromatography system (Sorbtech, 220 g silica column) to give (3-(triphenylsilyl)phenyl)boronic acid (4.40 g, 57% yield) as a white solid.

[0226] Step 3: A mixture of (3-(triphenylsilyl)phenyl)boronic acid (2.40 g, 6.31 mmol, 1.0 equivalent), 2-chloro-4,6-dimethoxy-1,3,5-triazine (1.11 g, 6.31 mmol, 1.0 equivalent), and potassium carbonate (1.74 g, 12.62 mmol, 2.0 equivalent) in a mixture of 1,4-dioxane (30.0 mL) and water (10.0 mL) was bubbled under nitrogen for 15 minutes. While bubbling for an additional 5 minutes, tetrakis(triphenylphosphine)palladium (0.73 g, 0.63 mmol, 0.1 equivalent) was added, and the mixture was stirred at 75 °C for 17 hours. The mixture was then poured into water (40 mL), extracted with dichloromethane (2 × 120 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by gradient elution with 10 to 50% ethyl acetate / hexane on an Interchim automated chromatography system (Sorbtech, 80 g silica column) to give 2,4-dimethoxy-6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine (2.51 g, 79% yield) as a white solid.

[0227] Step 4: Sodium hydroxide (5.90 g, 148 mmol, 6.0 equivalent) in water (50 mL) was added to a solution of 2,4-dimethoxy-6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine (11.7 g, 24.60 mmol, 1.0 equivalent) in THF (150 mL). The mixture was heated to reflux and maintained for 30 hours. LC / MS analysis indicated complete conversion to the monodemethylated intermediate. The mixture was cooled to room temperature, and the pH was adjusted to 7 using concentrated hydrochloric acid. The mixture was concentrated under reduced pressure to give a white solid. 1 M hydrochloric acid (200 mL) was added, and the mixture was heated to reflux for 16 hours. After cooling to ambient temperature, the mixture was filtered, and the solid was washed with water. The solid was then dried in a vacuum oven at 50 °C for 17 hours. The crude product was purified in two batches using an Interchim automated chromatography system (Sorbtech, 220 g silica column) with a gradient elution of 0 to 5% methanol / dichloromethane to give 6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine-2,4-diol (8.53 g, 77% yield) as a white solid.

[0228] Step 5: Phosphorus oxychloride (17.6 mL, 188 mmol, 24.0 equivalents) was added to a solution of 6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine-2,4-diol (3.51 g, 7.84 mmol, 1.0 equivalents) in anhydrous toluene (79 mL). The mixture was heated to reflux and maintained for 50 hours, then cooled to room temperature and concentrated under reduced pressure. The residue was absorbed in ethyl acetate (400 mL) and washed with saturated aqueous sodium bicarbonate solution (2 × 100 mL) and saturated brine (100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 2,4-dichloro-6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine (3.90 g, quantitative yield).

[0229] Step 6: At -78°C, add 2.5 M n-butyllithium (7.84 mL, 19.60 mmol, 2.5 equivalents) from hexane to 5 mL over 2 minutes. H -benzo[ d Benzo[4,5]imidazo[1,2-a]imidazolium (4.06 g, 19.60 mmol, 2.5 equivalents) was added to a stirred solution of anhydrous THF (75 mL). The mixture was allowed to warm to ambient temperature and then added to a solution of 2,4-dichloro-6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine (3.80 g, 7.84 mmol, 1.0 equivalents) in anhydrous THF (30 mL). After 20 hours, the mixture was poured into water (200 mL) and stirred for 2 hours. The solid was filtered, washed with water, and then dried in a vacuum oven at 50 °C for 18 hours. The resulting solid was then wet-milled with methanol (200 mL) for 2 hours, filtered, and dried in a vacuum oven. The resulting solid was then wet-milled, filtered, and dried sequentially with methanol (200 mL), ethanol (200 mL), isopropanol (200 mL), and dichloromethane (3 × 200 mL). The resulting solid was then refluxed in toluene (2 × 200 mL), filtered, and dried overnight in a vacuum oven at 50 °C to give 5,5'-(6-(3-(triphenylsilyl)phenyl)-1,3,5-triazine-2,4-diyl)bis(5 H -benzo[ d ]Benzo[4,5]imidazo[1,2-a]imidazo(EH-10) (2.86 g, 44% yield).

[0230] The compounds used in the OLEDs used in the experiments:

[0231] , , , , , , , ,

[0232] , , , , , , ,

[0233]

[0234] OLEDs are grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer having a sheet resistivity of 15 Ω / sq. Before any organic layer deposition or coating, the substrate is degreased with a solvent, then treated with oxygen plasma at 100 mTorr and 50 W for 1.5 minutes and with UV ozone for 5 minutes. The devices in Tables 1 and 2 are fabricated by thermal evaporation in a high vacuum (<10 Ω·cm). -6 The devices were manufactured in a [missing information - likely a specific process or method]. The anode electrode was 750 Å indium tin oxide (ITO). All devices were immediately sealed with a glass cap and epoxy resin in a nitrogen glove box (H2O and O2 < 1 ppm) after fabrication, with a desiccant incorporated inside the enclosure. Doping percentages are volume percentages. The device performance of Examples 1 to 13 and Comparative Examples 1 and 2 is shown in Tables 1 and 2. The voltage, EQE, and LT90 values ​​of Examples 1 to 9 relative to Comparative Example 1 are reported. The voltage, EQE, and LT90 values ​​of Examples 10 to 13 relative to Comparative Example 2 are reported.

[0235] The organic layer of device example 1 consists of the following components in sequence: an ITO surface, 100 Å compound 1 (HIL), 250 Å compound 2 (HTL), 50 Å HH-3 (EBL), 300 Å HH-3 doped with 40% EH-1 and 12% compound 3 (EML), 50 Å EH-1 (BL), 300 Å compound 4 doped with 35% compound 5 (ETL), 10 Å compound 5 (EIL), followed by 1,000 Å Al (cathode).

[0236] The structures of apparatus examples 2 to 9 are the same as those of example 1, except that EH-1 is replaced by EH-2 to EH-9 respectively. The structure of apparatus comparative example 1 is the same as that of example 1, except that EH-1 is replaced by that of comparative example 1.

[0237] Table 1: Performance of devices with HH-3

[0238]

[0239] The data above indicate that the combination of the silane electron transport host and the Pt complex biscarbazole hole transport host enhances the device lifetime. As co-hosts, EH-1 to EH-9 all exhibit longer lifetimes than the comparative compound (Comparative Example 1). The 1.12 to 2.97 times longer lifetimes of EH-1 to EH-9 exceed any value attributable to experimental error and represent a significant improvement. Given that EH-1 to EH-9 have a similar structure to Comparative Example A, differing only in silane substitution, the significant performance improvement observed in the above data is unexpected. Without being bound by any theory, this improvement compared to the comparative compound can be attributed to reduced bimolecular interactions of the silane-substituted host.

[0240] The organic layer of device example 10 consists of the following components in sequence: an ITO surface, 100 Å compound 1 (HIL), 250 Å compound 2 (HTL), 50 Å HH-3 (EBL), 300 Å HH-1 (EML) doped with 40% EH-9 and 12% compound 3, 50 Å EH-9 (BL), 300 Å compound 4 (ETL) doped with 35% compound 5, 10 Å compound 5 (EIL), followed by 1,000 Å Al (cathode).

[0241] The structures of apparatus examples 10 to 13 are the same as those of example 1, wherein HH-1 is replaced by HH-2 to HH-4 respectively. The structure of apparatus comparative example 2 is the same as that of example 1, but wherein HH-1 is replaced by that of comparative example 2.

[0242] Table 2: Performance of devices with EH-9

[0243]

[0244] The data above indicate that the combination of the silane electron transport host and the Pt complex-based biscarbazole hole transport host enhances the device lifetime. As co-hosts, HH-1 to HH-4 all exhibit longer lifetimes than the comparative compound (Comparative Example 2). The 1.53 to 2.65 times longer lifetimes of HH-1 to HH-4 exceed any value attributable to experimental error and represent a significant improvement. Given that HH-1 to HH-4 have a similar structure to Comparative Example 2, with the main difference being the inclusion of biscarbazole, the significant performance improvement observed in the above data is unexpected. Without being bound by any theory, this improvement can be attributed to the improved hole transport capability of the biscarbazole moiety compared to the monocarbazole moiety.

[0245] Figure 3The normalized phosphorescence emission spectra of EH9 and EH10 are shown. The phosphorescence emission spectra of EH-9 and EH-10 were measured by gated emission measurements on a Horiba Fluorolog-3 spectrophotometer. The samples were excited at 300 nm using a 20 ms delay and a 60 ms acquisition window.

[0246] Figure 3 The above data indicate a significant increase in the triplet energy of EH-10 compared to EH-9. The triplet emission spectrum of EH-10 exhibits a first emission peak at 403 nm, compared to 416 nm for EH-9. The 13 nm blue shift of EH-10 compared to EH-9 exceeds any value attributable to experimental error and represents a significant improvement. Given that EH-10 has a similar structure to EH-9, differing only in that the carbazole is replaced by a 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazolium group, the significant performance improvement observed in the above data is unexpected. Without being bound by any theory, this improvement can be attributed to the weaker conjugation of bimbim compared to carbazole.

Claims

1. A compound having the following formula: ， Where X 5 -X 20 Each can be either C or N independently; R 6 R 7 R 8 R 9 and R 10 Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and Where R 10 It is a substituted biphenyl; The substituted biphenyl is substituted with at least one carbazole.

2. The compound according to claim 1, wherein the substituted biphenyl R 10 The substituted biphenyl is bonded at a first site, and the substituted biphenyl is substituted with at least one carbazole at a second site, wherein the first site is located at the para position of the phenyl-phenyl bond of the substituted biphenyl, the second site is located at the para position of the phenyl-phenyl bond of the substituted biphenyl, or both.

3. The compound according to claim 1, wherein the substituted biphenyl R 10 It is substituted with at least two carbazole groups.

4. The compound according to claim 1, wherein the substituted biphenyl R 10 Substituted with unsubstituted carbazole.

5. The compound according to claim 1, wherein the substituted biphenyl R 10 It is dicarbazole biphenyl.

6. The compound according to claim 1, wherein the substituted biphenyl R 10 Each phenyl group is substituted with at least one carbazole.

7. The compound according to claim 1, wherein the substituted biphenyl R 10 At least one phenyl group is substituted with at least two carbazole groups.

8. The compound according to claim 1, wherein the substituted biphenyl R 10 It is a [1,1'-biphenyl]-4-yl group substituted with at least one carbazole.

9. The compound according to claim 1, wherein at least one carbazole is substituted at the ortho position of the biphenyl bond.

10. The compound of claim 1, wherein at least two carbazoles are substituted at the ortho position of the biphenyl bond.

11. The compound of claim 1, wherein the compound comprises 3,9-dicarbazole.

12. The compound of claim 1, wherein the compound comprises at least four carbazole groups.

13. The compound of claim 1, wherein the compound is partially or completely deuterated.

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

15. An organic light-emitting device (OLED) comprising: an anode; a cathode; and an emitting layer disposed between the anode and the cathode, the emitting layer comprising a host compound, wherein the host compound has the formula... ， Where X 5 -X 20 Each can be either C or N independently; R 6 R 7 R 8 R 9 and R 10 Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and Where R 10 It is a substituted biphenyl; The substituted biphenyl is substituted with at least one carbazole.

16. The OLED of claim 15, wherein the host compound is selected from the group consisting of: and .

17. The OLED of claim 15, wherein the emitting layer comprises another compound, and the other compound is also a common body comprising chemical groups selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, pyridine, pyrimidine, triazine, 5,9-dioxa-13b-boronanaphthene[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenene, and aza-(5,9-dioxa-13b-boronanaphthene[3,2,1-de]anthracene).

18. A consumer product including an organic light-emitting device (OLED), the OLED comprising: an anode; a cathode; and an emitting layer disposed between the anode and the cathode, the emitting layer comprising a host compound, wherein the host compound has the formula... , Where X 5 -X 20 Each can be either C or N independently; R 6 R 7 R 8 R 9 and R 10 Each is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxoboryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphinyl, and combinations thereof; and Where R 10 It is a substituted biphenyl; The substituted biphenyl is substituted with at least one carbazole.

19. The consumer product of claim 18, wherein the compound is selected from the group consisting of: and .

20. The consumer product of claim 18, wherein the consumer product is selected from the group consisting of: flat panel 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, laser printers, telephones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays, 3D displays, virtual reality or augmented reality displays, vehicles, large-area walls, theater or stadium screens, and signs.

21. The consumer product of claim 18, wherein the emission layer comprises another compound, and the other compound is also a co-body comprising a chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, pyridine, pyrimidine, triazine, 5,9-dioxa-13b-boronanaphthene[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenene, and aza-(5,9-dioxa-13b-boronanaphthene[3,2,1-de]anthracene).

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