Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Provided is an organic compound having a central structure comprising two aromatic 6-membered rings fused together via a 5-membered ring containing an atom selected from the group consisting of O, S and Se. Formulations comprising these organic compounds are also provided. Also provided are organic light emitting devices (OLEDs) and related consumer products using these organic compounds.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 620,898, filed on January 15, 2024, under 35 U.S.C. § 119(e), the entire content of which is incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to organic or metal coordination compounds and formulations and their various uses, including as emitters, hosts, sensitizers, charge transporters, or exciton transporters in devices such as organic light-emitting diodes and related electronic devices and consumer products. Background Art

[0004] For various reasons, optoelectronic devices using organic materials have become increasingly popular. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for a cost advantage over inorganic devices. Additionally, the inherent properties of organic materials, such as their flexibility, can make them more suitable for certain applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, organic scintillators, and organic photodetectors. For OLEDs, organic materials can have 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 attractive technology for applications such as displays, lighting, and backlighting.

[0006] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (referred to as "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, an OLED 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 emissions. The same technique can also be used for OLEDs. White OLEDs can be single-emissive layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. Summary of the Invention

[0007] In one aspect, the present disclosure provides a compound comprising a structure of Formula I:

[0008]

[0009] wherein Y A is selected from the group consisting of O, S, and Se;

[0010] Wherein X 1 to X 7 are each independently C or N;

[0011] Wherein R A and R B each independently represent mono-substitution to the maximum allowable number of substitutions, or no substitution;

[0012] Wherein R A and R B are each independently hydrogen or selected from the group consisting of: deuterium, fully or partially deuterated substituents, and substituted or unsubstituted carbazoles;

[0013] Wherein R 1 is a substituted or unsubstituted carbazole, or a substituted or unsubstituted azacarbazole;

[0014] Wherein the compound comprises at least three carbazole or azacarbazole moieties, and wherein at least two carbazole or azacarbazole moieties are joined to form a group selected from: 1,9-bicarbazole, 2,9-bicarbazole, 3,9-bicarbazole, and 4,9-bicarbazole and their aza-variants;

[0015] Wherein any two substituents may be joined or fused to form a ring.

[0016] In another aspect, the present disclosure provides a formulation of the compounds described herein.

[0017] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the compounds described herein.

[0018] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising the compounds described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Displays an organic light-emitting device.

[0020] Figure 2 Displays an inverted organic light-emitting device without an independent electron transport layer. DETAILED DESCRIPTION

[0021] A. Terms

[0022] Unless otherwise specified, the following terms used herein are defined as follows:

[0023] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed over" a second layer, the first layer is disposed further from the substrate. There may be other layers between the first and second layers unless it is specified that the first layer "contacts" the second layer. For example, even though there are various organic layers between the cathode and the anode, the cathode can still be described as being "disposed over" the anode.

[0024] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and / or deposited from a liquid medium.

[0025] As used herein, and as would be generally understood by one of ordinary skill in the art, if a first energy level is closer to the vacuum level, then the first "highest occupied molecular orbital" (HOMO) or "lowest unoccupied molecular orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram where the top is the vacuum level, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0026] As used herein, and as would be generally understood by one of ordinary skill in the art, if a first work function has a higher absolute value, then the first work function is "greater than" or "higher than" a second work function. Since the work function is typically measured as a negative number relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram where the top is the vacuum level, a "higher" work function is illustrated as being further from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than the work function.

[0027] The present disclosure may describe layers, materials, regions, and devices in terms of the color of the light they emit. Generally, as used herein, an emission region described as producing a particular color of light may include one or more emission layers disposed over one another in a stacked manner.

[0028] As used herein, a "NIR," "red," "green," "blue," or "yellow" layer, material, region, or device refers to a layer, material, region, or device that emits light in a wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, or 540-600 nm, respectively, or a layer, material, region, or device having the highest emission spectrum peak in the corresponding wavelength region. In some arrangements, separate regions, layers, materials, or devices may provide separate "deep blue" and "light blue" emissions. As used herein, a "deep blue" emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of a "light blue" emission component. Typically, the peak emission wavelength of the "light blue" emission component is in the range of about 465-500 nm, and the peak emission wavelength of the "deep blue" emission component is in the range of about 400-470 nm, but these ranges may vary for some configurations.

[0029] In some arrangements, a color-changing layer is provided that converts, modifies or changes the color of light emitted by another layer to an emission having a different wavelength. This color-changing layer can be configured to shift the wavelength of light emitted by another layer by a defined amount, as measured by the difference between the wavelength of the emitted light and the wavelength of the resulting light. In general, there are two types of color-changing layers: color filters that modify the spectrum by removing light of non-desired wavelengths, and color-changing layers that convert higher energy photons into lower energy. For example, there may be a "red" filter to filter the input light to remove light with wavelengths outside the range of about 580-700nm. A component of "color" refers to a component that produces or otherwise emits light having a specific color as previously described when activated or used. For example, a "first emission region of a first color" and a "second emission region of a second color different from the first color" describe two emission regions that emit two different colors as previously described when activated within the device.

[0030] As used herein, emissive materials, layers, and regions may be distinguished from each other and from other structures based on the light that the material, layer, or region initially produces as opposed to the light that the same or different structure ultimately emits. Initial light generation is typically the result of a change in energy levels that results in photon emission. For example, an organic emissive material may initially produce blue light, which may be converted to red or green light by a color filter, quantum dots, or other structure, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initial emissive material, region, or layer may be referred to as the "blue" component, even if the sub-pixel is the "red" or "green" component.

[0031] In some cases, it may be preferable to describe the color of the component according to 1931 CIE coordinates, such as the color of the emission region, subpixel, color-changing layer, etc. For example, a yellow-emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. The shape in the 1931 CIE color space is constructed by tracing the locus between two color points and any other internal points. For example, the internal shape parameters for red, green, blue, and yellow can be defined as follows:

[0032]

[0033] The terms "halo", "halogen", and "halo group" may be used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0034] The term "acyl group" refers to a substituted carbonyl group (-C(O)-R s ).

[0035] The term "ester" refers to a substituted oxycarbonyl group (-O-C(O)-R s or -C(O)-O-R s ).

[0036] The term "ether" refers to an -OR s group.

[0037] The terms "sulfanyl" or "thioether" may be used interchangeably and refer to an -SR s group.

[0038] The term "selenoalkyl" refers to a -SeR s group.

[0039] The term "sulfinyl" refers to an -S(O)-R s group.

[0040] The term "sulfonyl" refers to an -SO2-R s group.

[0041] The term "phosphino group" refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include, but are not limited to, groups such as -P(R s )2 group or -PO(R s )2 group, where each R s can be the same or different.

[0042] The term "silyl group" refers to a group containing at least one silicon atom bonded to the relevant structure. Common examples of silyl groups include, but are not limited to, groups such as -Si(R s)3 groups, where each R s may be the same or different.

[0043] The term "germyl" refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl groups include, but are not limited to, groups such as -Ge(R s )3 groups, where each R s may be the same or different.

[0044] The term "boryl" refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boryl groups include, but are not limited to, groups such as -B(R s )2 groups or their Lewis adducts -B(R s )3 groups, where R s may be the same or different.

[0045] In each of the above, R s may be hydrogen or a substituent selected from the group consisting of general substituents as defined in this application. Preferred R s is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s is selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0046] The term "alkyl" refers to and includes both straight-chain and branched-chain alkyls having alkyl carbon atoms bonded to the relevant structure. Preferred alkyls are alkyls containing one to fifteen carbon atoms, preferably one to nine carbon atoms, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,3-dimethylpropyl, 1,1-dimethylpropyl, 2-ethylpropyl, 1,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, etc. Additionally, the alkyl may be further substituted.

[0047] The term "cycloalkyl" means and includes monocyclic, polycyclic, and spirocycloalkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are cycloalkyl groups having 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group may be further substituted.

[0048] The term "heteroalkyl" or "heterocycloalkyl" means an alkyl or cycloalkyl group having at least one carbon atom replaced by a heteroatom, respectively. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Additionally, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0049] The term "alkenyl" means and includes both straight-chain and branched-chain alkene groups. An alkenyl group is essentially an alkyl group having at least one carbon-carbon double bond in the alkyl chain, where one carbon atom is from the carbon-carbon double bond bonded to the relevant structure. A cycloalkenyl group is essentially a cycloalkyl group having at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" means an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally, at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those having two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be further substituted.

[0050] The term "alkynyl" means and includes both straight-chain and branched-chain alkyne groups. An alkynyl group is essentially an alkyl group having at least one carbon-carbon triple bond in the alkyl chain, where one carbon atom is from the carbon-carbon triple bond bonded to the relevant structure. Preferred alkynyl groups are alkynyl groups having two to fifteen carbon atoms. Additionally, the alkynyl group may be further substituted.

[0051] The terms "aralkyl" or "arylalkyl" are used interchangeably and mean an aryl-substituted alkyl group having alkyl carbon atoms bonded to the relevant structure. Additionally, the aralkyl group may be further substituted.

[0052] The term "heterocyclic group" means and includes aromatic and non-aromatic ring groups containing at least one heteroatom. Optionally, at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably O, S, N, or B. Heteroaromatic ring groups can be used interchangeably with heteroaryl groups. Preferred non-aromatic heterocyclic groups are non-aromatic heterocyclic groups containing 3 to 10 ring atoms, preferably non-aromatic heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom, and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. Additionally, the heterocyclic group can be further substituted or fused.

[0053] The term "aryl" means and includes both monocyclic and polycyclic aromatic hydrocarbon groups. The polycyclic can have two or more rings, where two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are aryl groups containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six, ten, twelve, fourteen, or eighteen carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, fluorene, phenanthrene, pyrene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, and naphthalene. Additionally, the aryl group can be further substituted or fused, such as but not limited to fluorene.

[0054] The term "heteroaryl" refers to and includes both monocyclic aromatic groups and polycyclic aromatic ring systems having at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The polycyclic heterocyclic system may have two or more aromatic rings, where two atoms are common to two adjacent rings (the rings are "fused"), and at least one of the rings is a heteroaryl. The polycyclic heteroaromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryls include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborane, borazine, 5λ 2 ,9λ 2 -diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxab-13b-boraphenanthro[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxab-13b-boraphenanthro[3,2,1-de]anthracene. Additionally, the heteroaryl may be further substituted or fused.

[0055] Among the aryls and heteroaryls listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2-Diazab-13b-boraphenanthro[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boraphenanthro[3,2,1-de]anthracene groups, and their corresponding aza analogs are of particular interest.

[0056] In many cases, the general substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0057] In some cases, the preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0058] In some cases, the more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0059] In some cases, the even more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

[0060] In still other cases, the most preferred general substituents are selected from the group consisting of: deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0061] The terms "substituted" and "substitution" mean that a substituent other than H is bonded to the relevant position, such as carbon or nitrogen. For example, when R 1 represents monosubstitution, then one R 1 must not be H (i.e., substitution). Similarly, when R 1 represents disubstitution, then both R 1 must not be H. Similarly, when R 1 represents zero or no substitution, R 1 can, for example, be hydrogen at all available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atom in pyrrole, or for ring atoms with fully saturated valences, it only means none, such as the nitrogen atom in pyridine. The maximum possible number of substitutions in the ring structure will depend on the total number of available valences in the ring atoms.

[0062] As used herein, "in combination" means that one or more members of an applicable list are combined to form a known or chemically stable arrangement that can be envisioned by one of ordinary skill in the art from the applicable list. By way of example, an alkyl group and deuterium can be combined to form a partially or fully deuterated alkyl group; a halogen and an alkyl group can be combined to form a haloalkyl substituent; and a halogen, an alkyl group, and an aryl group can be combined to form a haloaryalkyl group. In one example, the term substituted includes combinations of two to four of the listed groups. In another example, the term substituted includes combinations of two to three groups. In yet another example, the term substituted includes combinations of two groups. Preferred combinations of substituents are combinations that contain up to fifty atoms that are not hydrogen or deuterium, or combinations that include up to forty atoms that are not hydrogen or deuterium, or combinations that include up to thirty atoms that are not hydrogen or deuterium. In many instances, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0063] As used herein, the term "aza" in fragments such as aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C-H groups in the corresponding aromatic ring can be replaced by a nitrogen atom. For example and without any limitation, aza-triphenylene encompasses dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as set forth herein.

[0064] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. By way of example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951, and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entireties) describe the preparation of deuterium-substituted organometallic complexes. Further reference to Ming Yan et al., Tetrahedron 2015, 71, 1425 - 30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744 - 65 (which are incorporated herein by reference in their entireties) describe effective routes for the deuteration of methylene hydrogens in benzylamines and for the replacement of aromatic ring hydrogens with deuterium, respectively.

[0065] As used herein, any specifically listed substituent, such as but not limited to methyl, phenyl, pyridyl, etc. includes its non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituents such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc. also include their non-deuterated, partially deuterated, and fully deuterated forms. Unless otherwise specified, atoms in a chemical structure that do not have valences completely filled by H or D should be considered to include their non-deuterated, partially deuterated, and fully deuterated forms. For example, the chemical structure is meant to include C6H6, C6D6, C6H3D3, and any other of its partially deuterated variants. Some common basic or fully deuterated groups include but are not limited to CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0066] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written as if it were the fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were the entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attached fragments are considered equivalent.

[0067] In some cases, a pair of substituents in a molecule may optionally be joined or fused to form a ring. Preferred rings are five- to nine-membered carbocyclic or heterocyclic rings, including cases where part of the ring formed by the pair of substituents is saturated and cases where part of the ring formed by the pair of substituents is unsaturated. In still other cases, a pair of adjacent substituents may optionally be joined or fused to form a ring. As used herein, "adjacent" means that the two substituents involved can be adjacent to each other on the same ring or on two neighboring rings having the two closest available substitutable positions (such as the 2,2'-positions in biphenyl or the 1,8-positions in naphthalene).

[0068] B. Compounds of the Present Disclosure

[0069] In one aspect, the present disclosure provides a compound comprising a structure of Formula I:

[0070]

[0071] wherein Y A is selected from the group consisting of O, S, and Se;

[0072] wherein X 1 to X 7 are each independently C or N;

[0073] wherein R A and R B each independently represent mono-substituted to the maximum allowable number of substitutions, or unsubstituted;

[0074] wherein RA and R B are each independently hydrogen or selected from the group consisting of: deuterium, fully or partially deuterated substituents, and substituted or unsubstituted carbazoles;

[0075] wherein R 1 is a substituted or unsubstituted carbazole, or a substituted or unsubstituted azacarbazole;

[0076] wherein the compound comprises at least three carbazole or azacarbazole moieties, and wherein at least two carbazole or azacarbazole moieties are joined to form a group selected from: 1,9-bicarbazole, 2,9-bicarbazole, 3,9-bicarbazole, and 4,9-bicarbazole and their aza-variants;

[0077] wherein any two substituents may be joined or fused to form a ring.

[0078] In some embodiments, neither R A nor R B is a substituted or unsubstituted C6-C 12 aryl.

[0079] In some embodiments, no carbazole moiety is joined to a ring group other than ring B by a C-C bond.

[0080] In some embodiments, the compound is not:

[0081]

[0082] In some embodiments, Y A is O.

[0083] In some embodiments, Y A is S.

[0084] In some embodiments, Y A is Se.

[0085] In some embodiments, at least one of X 1 to X 7 is N.

[0086] In some embodiments, exactly one of X 1 to X 7 is N.

[0087] In some embodiments, at least two of X 1 to X 7 are N.

[0088] In some embodiments, all of X 1 to X 7 are C.

[0089] In some embodiments, at least one carbazole moiety is attached to Ring A.

[0090] In some embodiments, at least one carbazole moiety is attached to X 1 .

[0091] In some embodiments, at least one carbazole moiety is attached to X 2 .

[0092] In some embodiments, at least one carbazole moiety is attached to X 3 .

[0093] In some embodiments, at least one carbazole moiety is attached to X 4 .

[0094] In some embodiments, at least one carbazole moiety is attached to X 5 .

[0095] In some embodiments, at least one carbazole moiety is attached to X 6 .

[0096] In some embodiments, at least one carbazole moiety is attached to X 7 .

[0097] In some embodiments, at least two carbazole moieties are joined to form 1,9-bicarbazole.

[0098] In some embodiments, at least two carbazole moieties are joined to form 2,9-bicarbazole.

[0099] In some embodiments, at least two carbazole moieties are joined to form 3,9-bicarbazole.

[0100] In some embodiments, at least two carbazole moieties are joined to form 4,9-bicarbazole.

[0101] In some embodiments, the compound comprises exactly three carbazole groups.

[0102] In some embodiments, the compound comprises at least four carbazole groups.

[0103] In some embodiments, the compound comprises exactly four carbazole groups.

[0104] In some embodiments, R 1 is a substituted or unsubstituted tricarbazole group.

[0105] In some embodiments, R 1 is a substituted or unsubstituted bicarbazole group and at least one of R A and R B is a substituted or unsubstituted carbazole.

[0106] In some embodiments, R A and R B at least one of which is a substituted or unsubstituted carbazole or azacarbazole group.

[0107] In some embodiments, R A and R B at least one of which is a substituted or unsubstituted bi-carbazole or azabi-carbazole group.

[0108] In some embodiments, at least one R A is a carbazole group.

[0109] In some embodiments, at least one R A is a bi-carbazole group.

[0110] In some embodiments, at least one R A is a fully or partially deuterated substituent.

[0111] In some embodiments, R A and R B at least one of which is deuterium.

[0112] In some embodiments, one of R A and R B is a substituted or unsubstituted carbazole group and the remaining sites are all deuterium.

[0113] In some embodiments, the compound does not contain the structure:

[0114]

[0115] In some embodiments, the compound is selected from the group consisting of:

[0116]

[0117]

[0118]

[0119]

[0120] wherein X 8 to X 31 are each independently C or N;

[0121] wherein R C 、R D 、R E 、R F 、R G 、R H and RI independently represent mono - substitution to the maximum allowable number of substitutions, or no substitution;

[0122] where each R C 、R D 、R E 、R F 、R G 、R H and R I is independently hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boranyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selanyl and combinations thereof.

[0123] In some embodiments, the compounds are selected from the group consisting of: compound W1-(Ai)(Bj)(Yk), compound W2-(Ai)(Bj)(Rl)(Yk), where W1 is an integer from 1 to 12, W2 is an integer from 13 to 42, each i is an integer from 1 to 24, each j is an integer from 1 to 15, each l is an integer from 1 to 45 and each k is an integer from 1 to 3, each Ai is independently selected from the group consisting of A1 to A24, each Bj is independently selected from the group consisting of B1 to B15, each Rl is independently selected from the group consisting of R1 to R45, each Yk is independently selected from the group consisting of Y1 to Y3, and each of compound 1-(A1)(B1)(Y1) to compound 12-(A24)(B15)(Y3) and compound 13-(A1)(B1)(R1)(Y1) to compound 42-(A24)(B15)(R45)(Y3) is defined in the following table:

[0124]

[0125]

[0126]

[0127]

[0128] where Y1 is O, Y2 is S and Y3 is Se, and where A1 to A24 have the following structures:

[0129]

[0130]

[0131] where B1 to R15 have the following structures:

[0132]

[0133]

[0134] Among them, R1 to R45 have the following structure:

[0135]

[0136]

[0137]

[0138] In some embodiments, the compound is selected from the group consisting of the structures in the following List 1:

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] In some embodiments, the compound mainly consists of Formula I.

[0155] In some embodiments, the compound has the structure of Formula I.

[0156] In some embodiments, the compounds of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its ordinary meaning and includes the percentage of all possible hydrogen atoms (e.g., positions that are either hydrogen or deuterium) occupied by deuterium atoms. In some embodiments, one or more hole-transporting moieties are partially or fully deuterated. In some embodiments, one or more electron-transporting moieties are partially or fully deuterated. In some embodiments, one or more fused ring systems are partially or fully deuterated. In some embodiments, one or more non-fused rings are partially or fully deuterated. In some embodiments, one or more rings or fused rings containing one or more heteroatoms are partially or fully deuterated. In some embodiments, one or more fused or non-fused phenyl rings are partially or fully deuterated. In some embodiments, one or more alkyl or cycloalkyl groups are partially or fully deuterated.

[0157] In yet another aspect of the present disclosure, a formulation comprising a novel compound disclosed herein is described. The formulation can include one or more components disclosed herein selected from the group consisting of solvents, emitters, hosts, hole injection materials, hole transporting materials, electron blocking materials, hole blocking materials, and electron transporting materials.

[0158] The present disclosure encompasses any chemical structure comprising a novel compound of the present disclosure or its monovalent or polyvalent variants. In other words, the compounds of the present invention or their monovalent or polyvalent variants can be part of a larger chemical structure. Such chemical structures can 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 the same moiety as the compound, but in which one hydrogen has been removed and replaced with a bond connecting to the remainder of the chemical structure. As used herein, a "polyvalent variant of a compound" refers to the same moiety as the compound, but in which more than one hydrogen has been removed and replaced with one or more bonds connecting to the remainder of the chemical structure. In the case of supramolecules, the compounds of the present invention can also be incorporated into supramolecular complexes non-covalently. As used in this context, the description that structure A contains moiety B means that structure A includes the structure of moiety B, and the structure of moiety B does not include the H or D atoms that can be attached to moiety B. This is because at least one H or D on a given partial structure must be replaced with a substituent such that moiety B can be part of structure A, and after it becomes part of structure A, one or more of the H or D on the given partial structure of moiety B can be further substituted.

[0159] C. OLEDs and Devices of the Present Disclosure

[0160] In another aspect, the present disclosure also provides an OLED device, which includes a first organic layer containing the compounds disclosed in the above compound section of the present disclosure.

[0161] In some embodiments, the OLED includes: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer contains the compounds described herein.

[0162] In some embodiments, the organic layer can be an emission layer. In some embodiments, the organic layer is selected from the group consisting of: HIL, HTL, EBL, EML, HBL, ETL, and EIL.

[0163] In some embodiments, the compound can be a host, and the first organic layer can be an emission layer containing a phosphorescent or fluorescent emitter. As used herein, phosphorescence generally refers to photon emission when the electron spin quantum number changes, that is, the initial and final states of the emission have different electron spin quantum numbers, such as from the T1 to the S0 state. Most Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if the exciplex formation involves a triplet emitter, such exciplexes can also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to photon emission when the electron spin quantum number remains unchanged, such as from the S1 to the S0 state, or from the D1 to the D0 state. The fluorescent emitter can be a delayed fluorescence or non-delayed fluorescence emitter. Depending on the spin state, the fluorescent emitter can be a singlet emitter or a doublet emitter or other multiplet emitters. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not depend on the collision of two triplets, but on the thermal population between the triplet and the singlet excited state. Thermal energy can activate the triplet transition back to the singlet. This type of delayed fluorescence is also called TADF. The characteristics of E-type delayed fluorescence can be seen in exciplex systems or single compounds. Without being bound by theory, it is believed that TADF emission requires a small singlet-triplet energy gap (ΔE) of less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. S-T) compounds or excited state complexes. There are two main types of TADF emitters, one called donor-acceptor type TADF and the other called multi-resonant (MR) TADF. Generally, single compound donor-acceptor TADF compounds are constructed by connecting an electron donor moiety (such as an amino or carbazole derivative) and an electron acceptor moiety (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited state complex can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, the MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials can also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 for delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.

[0164] In some embodiments, the compound is a host, and the organic layer is an emissive layer containing a phosphorescent or fluorescent material.

[0165] In some embodiments, the emissive dopant can be a phosphorescent or fluorescent material.

[0166] In some embodiments, the non-emissive dopant can also be a phosphorescent or fluorescent material.

[0167] In some embodiments, the OLED can include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0168] In some embodiments, the phosphorescent material is an emitter that emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the energy of the phosphorescent material transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further includes a receptor. In some embodiments, the phosphorescent material forms an excited state complex with another material (such as a host material, an emitter material) within the OLED.

[0169] In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is an emitter that emits light within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material does not emit light within the OLED. In some embodiments, the energy of the non-delayed fluorescent material or the delayed fluorescent material transfers its excited state to another material within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescent material or the delayed fluorescent material is a receptor, and the OLED further includes a sensitizer.

[0170] In some embodiments, the compound can be a receptor, and the OLED can further include a sensitizer selected from the group consisting of: delayed fluorescence materials, phosphorescent materials, and combinations thereof.

[0171] In some embodiments, the compound can be a non-delayed fluorescence emitter, a delayed fluorescence emitter, or a component as a non-delayed fluorescence emitter or a delayed fluorescence emitter in an exciplex. In some embodiments, the emission of the compound at room temperature has a full width at half maximum (FWHM) equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. A narrower FWHM means better color purity for OLED display applications.

[0172] In some embodiments, the compound is a host and the OLED includes a receptor as an emitter and a sensitizer selected from the group consisting of delayed fluorescence materials, phosphorescent materials, and combinations thereof; wherein the sensitizer transfers energy to the receptor.

[0173] In some embodiments, the phosphorescent material can be a metal coordination complex having a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond. In some embodiments, the metal is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt. In some embodiments, the metal is Cu, Ag, or Au. In some embodiments, the phosphorescent material has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0174] wherein L 1 , L 2 , and L 3 can be the same or different;

[0175] wherein x is 1, 2, or 3;

[0176] wherein y is 0, 1, or 2;

[0177] wherein z is 0, 1, or 2;

[0178] wherein x + y + z is the oxidation state of the metal M;

[0179] wherein L 1 is selected from the group consisting of structures in the following ligand list:

[0180]

[0181]

[0182]

[0183] Where each L 2 and L 3 are independently selected from the group consisting of: and the structures in the ligand list; wherein:

[0184] M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;

[0185] T is selected from the group consisting of B, Al, Ga, and In;

[0186] K 1 ' is a direct bond or is selected from the group consisting of NR e , PR e , O, S, and Se;

[0187] Each Y 1 to Y 15 are independently selected from the group consisting of carbon and nitrogen;

[0188] Y' is selected from the group consisting of 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 ;

[0189] R e and R f may be fused or joined to form a ring;

[0190] Each R a , R b , R c , and R d may independently represent mono-substituted to the maximum possible number of substitutions, or unsubstituted;

[0191] Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e , and R fis independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; and

[0192] wherein any two substituents may be fused or joined to form a ring or form a multidentate ligand.

[0193] In some embodiments, the phosphorescent material has a chemical formula selected from the group consisting of: Ir(L A )3, Ir(L A )(L B )2, Ir(L A )2(L B ), Ir(L A )2(L C ), Ir(L A )(L B )(L C ), and Pt(L A )(L B );

[0194] wherein L A , L B , and L C are different from each other in the Ir compound;

[0195] wherein L A and L B may be the same or different in the Pt compound; and

[0196] wherein L A and L B may be linked to form a tetradentate ligand in the Pt compound.

[0197] In some embodiments, the phosphorescent material is selected from the group consisting of the following dopant group 1:

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] wherein

[0205] each of X 96 to X 99 is independently C or N;

[0206] each Y100 Independently selected from the group consisting of NR", O, S, and Se;

[0207] R 10a R 20a R 30a R 40a and R 50a each independently represents mono-substituted up to the maximum number of substitutions, or unsubstituted;

[0208] R, R', R", R 10a R 11a R 12a R 13a R 20a R 30a R 40a R 50a R 60 R 70 R 97 R 98 and R 99 each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0209] In some embodiments, the phosphorescent material is selected from the group consisting of the following dopant group 2:

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218] wherein:

[0219] each Y 100 is independently selected from the group consisting of NR", O, S, and Se;

[0220] L is independently selected from the group consisting of a direct bond, BR", BR"R"', NR", PR", O, S, Se, C═O, C═S, C═Se, C═NR", C═CR"R"', S═O, SO2, CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0221] X 100 and X 200 in each occurrence is selected from the group consisting of O, S, Se, NR", and CR"R"';

[0222] Each R A" 、R B" 、R C" 、R D" 、R E" and R F" independently represents mono - substitution up to the maximum number of substitutions, or no substitution;

[0223] R, R', R", R"', R A1 ', R A2 ', R A" 、R B" 、R C" 、R D" 、R E" 、R F" 、R G" 、R H" 、R I" 、R J" 、R K" 、R L" 、R M" and R N" each of which is independently hydrogen or a substituent selected from the group of general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0224] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom can be replaced by N to form a nitrogen - containing heterocycle. In some embodiments, the maximum number of N atoms in a ring is 1 or 2. In some embodiments of the above dopant group 2, the Pt atom in each formula can be replaced by a Pd atom.

[0225] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non - metal complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag, or Au complex.

[0226] In some embodiments of the OLED, the delayed fluorescence material has the formula M(L 5 )(L 6 ), where M is Cu, Ag, or Au, L 5 and L 6 are different, and L 5 and L 6 are independently selected from the group consisting of:

[0227]

[0228]

[0229]

[0230] where A 1 to A 9 are each independently selected from C or N;

[0231] Each R P 、R Q and R U independently represents mono-substituted up to the maximum number of substitutions, or unsubstituted;

[0232] where each R P 、R P 、R U 、R SA 、R SB 、R RA 、R RB 、R RC 、R RD 、R RE and R RF are independently hydrogen or a substituent selected from the group of general substituents defined herein; any two substituents may be joined or fused to form a ring.

[0233] In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor moiety selected from the group consisting of:

[0234]

[0235]

[0236] where Y T 、Y U 、Y V and Y W are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2.

[0237] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of three carbon ring atoms together with their substituents can be replaced by N.

[0238] In some embodiments, the delayed fluorescence material comprises at least one acceptor moiety selected from the group consisting of: nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety as described herein can be directly connected, connected via a conjugated linking group or a non-conjugated linking group (e.g., sp 3 carbon or silicon atoms).

[0239] In some embodiments, the fluorescent material comprises at least one chemical moiety selected from the group consisting of:

[0240]

[0241]

[0242]

[0243] wherein Y F 、Y G 、Y H and Y I are each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO2;

[0244] wherein X F and X G are each independently selected from the group consisting of C and N.

[0245] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures, up to a total of three carbon ring atoms together with their substituents can be replaced by N.

[0246] In yet another aspect, the OLED of the present disclosure may further comprise an emission region containing a compound or a compound formulation as disclosed in the above compound section of the present disclosure. In some embodiments, the emission region may comprise a compound, or a formulation of the compounds described herein. In some embodiments, the emission region consists of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed of an emissive system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM can be obtained in U.S. Patent Application Publication No. 2023 / 0292605, the entire content of which is incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or formulation of compounds as disclosed in Parts A and D of the present disclosure.

[0247] In some embodiments, the OLEDs or emissive regions comprising the compounds of the present invention disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such a device comprises at least one pixel, wherein the at least one pixel comprises a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED that comprises a first emissive region. The second sub-pixel includes a second OLED that comprises a second emissive region. In some embodiments, the first and / or second OLEDs, the first and / or second emissive regions can be the same or different and each can independently have various device features and various embodiments of the compounds of the present invention included therein, as well as various combinations and sub-combinations of various device features and various embodiments of the compounds of the present invention included therein, as disclosed herein.

[0248] In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 ; the second emissive region is configured to emit light having a peak wavelength λ max2 In some embodiments, the difference between the peak wavelength λ max1 and λ max2 is at least 4 nm but within the same color. For example, light of light blue and dark blue as described above. In some embodiments, the first emissive region is configured to emit light having a peak wavelength λ max1 in a region of the visible spectrum of 400 - 500 nm, 500 - 600 nm, 600 - 700 nm; and the second emissive region is configured to emit light having a peak wavelength λ max2light. In some embodiments, the first emission region comprises (if more than one) a first number of emission layers deposited one on top of another; and the second emission region comprises (if more than one) a second number of emission layers deposited one on top of another; and the first number is different from the second number. In some embodiments, both the first emission region and the second emission region comprise phosphorescent materials that may be the same or different. In some embodiments, the first emission region comprises a phosphorescent material while the second emission region comprises a fluorescent material. In some embodiments, both the first emission region and the second emission region comprise fluorescent materials that may be the same or different.

[0249] In some embodiments, at least one pixel of the OLED or the emission region comprises a total of N sub-pixels; where the N sub-pixels comprise a first sub-pixel and a second sub-pixel; where each of the N sub-pixels comprises an emission region; and where the total number of emission regions within at least one pixel is equal to or less than N - 1. In some embodiments, the second emission region is identical to the first emission region; and each sub-pixel of at least one pixel comprises an emission region identical to the first emission region. In some embodiments, the full-color pixel arrangement may have a plurality of pixels comprising a first pixel region and a second pixel region; where at least one display characteristic of the first pixel region is different from the corresponding display characteristic of the second pixel region, and where at least one display characteristic is selected from the group consisting of: resolution, cavity mode, color, out-coupling, and color filter.

[0250] In some embodiments, the OLED is a stacked OLED comprising one or more charge generation layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emission region disposed above the first electrode, a first CGL disposed above the first emission region, a second emission region disposed above the first CGL, and a second electrode disposed above the second emission region. In some embodiments, the first emission region and / or the second emission region may have various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white light. In some embodiments, one or more of the emission regions in the pixelated OLED or the stacked OLED comprise a sensitizer and a receptor having various sensitization device characteristics and various embodiments of the inventive compounds disclosed herein. For example, the first emission region is included in the sensitization device while the second emission region is not included in the sensitization device; in some cases, both the first emission region and the second emission region are included in the sensitization device.

[0251] In some embodiments, the OLED can emit light with at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% from the plasmon mode. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emission layer serves as an enhancement layer. The enhancement layer includes a plasmonic material that exhibits surface plasmon resonance, the plasmonic material being non-radiatively coupled to the emitter material and transferring the excited state energy from the emitter material to the non-radiative mode of the surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance not exceeding a threshold distance from the organic emission layer, where due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant. The threshold distance is the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and the total radiative decay rate constant is equal to the photoluminescence yield of the emitter material in the absence of the enhancement layer.

[0252] In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the side opposite the organic emission layer above the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polariton. In some embodiments, this energy is scattered as photons into free space. In other embodiments, the energy is scattered from the surface plasmon mode of the device into other modes, such as but not limited to organic waveguide modes, substrate modes, or another waveguide mode. In some embodiments, one or more intermediate layers can be disposed between the enhancement layer and the outcoupling layer. Examples of the intermediate layer can be dielectric materials, including organic, inorganic, perovskite, oxides, and can include stacks and / or mixtures of these materials.

[0253] The enhancement layer changes the effective properties of the medium in which the emitter material resides, thereby causing any one or all of the following: reduced emissivity, changed emission line shape, angular variation of emission intensity, changed emitter material stability, changed OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, anode side, or both sides, or placing the enhancement layer itself as a CGL produces an OLED device that utilizes any of the above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, the OLEDs according to the present disclosure may further include any other functional layers common in OLEDs.

[0254] In some embodiments, the enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. In some embodiments, the plasmonic material includes at least one metal. In such embodiments, the metal may include at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has features of wavelength size arranged periodically, quasi-periodically, or randomly, or features of sub-wavelength size arranged periodically, quasi-periodically, or randomly.

[0255] In some embodiments, the out-coupling layer has features of wavelength size or sub-wavelength size arranged periodically, quasi-periodically, or randomly. In some embodiments, the out-coupling layer may be composed of a plurality of nanoparticles. In some embodiments, the out-coupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the out-coupling layer can be adjusted by at least one of the following: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed from at least one of the following: metal, dielectric material, semiconductor material, metal alloy, mixture of dielectric materials, stack or layer of one or more materials, and / or a core of one type of material coated with a shell of another type of material. In some embodiments, the out-coupling layer is composed of at least metal nanoparticles, where the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the out-coupling layer is formed by lithography.

[0256] In some embodiments of the plasmonic device, the emitter and / or host compound used in the emission layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0257] In yet another aspect, the present disclosure also provides a consumer product that includes an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer may include a compound or formulation of compounds as disclosed in the above compound portion of the present disclosure.

[0258] In some embodiments, a consumer product includes an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer can include the compounds described herein.

[0259] Generally, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the electrode having the opposite charge. When an electron and a hole are located on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. When the exciton relaxes through a light-emitting mechanism, light is emitted. In some cases, the exciton can be localized as an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, can also occur but are generally considered undesirable.

[0260] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. Device 100 can include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emission layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 can be fabricated by depositing the layers in sequence. The properties and functions of these various layers and exemplary materials are described in more detail in columns 6-10 of US 7,279,704, which is incorporated by reference.

[0261] Additional instances of each of these layers can be obtained. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of the emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entireties, disclose examples of cathodes that include a composite cathode having a thin layer of metal (such as Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of the blocking layer 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 entireties. Examples of the injection layer are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated herein by reference in its entirety.

[0262] Figure 2 Displays an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 can be fabricated by depositing the layers in sequence. Since the most common OLED configuration has a cathode disposed above the anode, and the device 200 has a cathode 215 disposed under the anode 230, the device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to the device 100 can be used in the corresponding layers of the device 200. Figure 2 Provides an example of how some of the layers can be omitted from the structure of the device 100.

[0263] Figure 1 and 2The simple layered structure described is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may 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 may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be completely omitted 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 of the examples provided herein describe the various layers as including a single material, it should be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Additionally, the layers may have various sub-layers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, the hole transport layer 225 transports holes and injects holes into the emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between the cathode and the anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials such as, for example, as described with respect to Figure 1 and 2 the different organic materials described.

[0264] Structures and materials not specifically described may also be used, such as an OLED containing a polymeric material (PLED), as disclosed, for example, in U.S. Patent No. 5,247,190 to Friend et al., which is incorporated herein by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, for example, as described in U.S. Patent No. 5,707,745 to Forrest et al., which is incorporated herein by reference in its entirety. The OLED structure may deviate from Figure 1 and 2 the simple layered structure described. For example, the substrate may include an angled reflective surface to improve out-coupling, such as the mesa structure described in U.S. Patent No. 6,091,195 to Forrest et al., and / or the dimpled structure described in U.S. Patent No. 5,834,893 to Bulovic et al., which are incorporated herein by reference in their entirety.

[0265] Unless otherwise specified, any one of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entirety), organic vapor phase deposition (OVPD) (as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably carried out in nitrogen or an inert atmosphere. For other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding (as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety) and patterning associated with some of the deposition methods such as inkjet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to be suitable for a particular deposition method. For example, branched or unbranched substituents such as alkyl and aryl groups having at least 3 carbons may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons may be used, and a range of 3 to 20 carbons is preferred. Materials having an asymmetric structure may have better solution processability than materials having a symmetric structure because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0266] Devices fabricated in accordance with embodiments of the present disclosure may further optionally include a barrier layer. One use of the barrier layer is to protect the electrodes and organic layers from damage by harmful substances in an environment exposed to, including moisture, vapor, and / or gases, etc. The barrier layer may be deposited on the substrate, on the electrodes, under the substrate, under the electrodes, beside the substrate, beside the electrodes, or on any other part of the device (including the edges). The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include 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 incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise multiple alternative layers of the following materials: polymeric materials and non-polymeric materials; organic materials and inorganic materials; or mixtures of polymeric materials and non-polymeric materials, an example of which is 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 entireties.

[0267] Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units), which can in turn be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels) that can be utilized by end-user product manufacturers. The electronic component modules can optionally include driving electronics and / or a power source. Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product that includes an OLED that includes a compound of the present disclosure in an organic layer of the OLED. The consumer product should include any kind of product that includes one or more light sources and / or one or more of certain types of visual displays. Some examples of the consumer product include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays having a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls that include a plurality of displays tiled together, theater or stadium screens, light therapy devices, and signage. A variety of control mechanisms can be used to control the devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as from 18 °C to 30 °C, and more preferably at room temperature (20 - 25 °C), but can be used outside of this temperature range (e.g., from -40 °C to +80 °C).

[0268] More 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.

[0269] 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 employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0270] In some embodiments, the OLED has one or more characteristics 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 includes a layer comprising carbon nanotubes. In some embodiments, the OLED further includes one or more quantum dots. Such quantum dots may be in the emissive layer or in other functional layers, such as a down-conversion layer.

[0271] In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. 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 less than 10 inches or an area 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.

[0272] Other materials used in OLEDs

[0273] The materials described herein are various examples of materials that can be used in specific layers of an OLED. It can also be used in combination with a wide variety of other materials present in the device. For example, the host materials disclosed herein can be used alone in the EML or in combination with a wide variety of other emitters, hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds and devices disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0274] a) Conductive dopants:

[0275] The charge transport layer can be doped with a conductive dopant to generally change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductive dopant, and an n-type conductive dopant is used in the electron transport layer. In some embodiments, the conductive dopant includes at least one chemical moiety selected from the group consisting of cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl extended by acyclic double bonds.

[0276] b) HIL / HTL:

[0277] The hole injection / transport materials used in the present disclosure are not particularly limited, and any compound can be used as long as the compound is commonly used as a hole injection / transport material. Examples of the materials include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; fluorocarbon-containing polymers; polymers with conductive dopants; conductive polymers such as PEDOT / PSS; self-assembled monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconducting organic compounds such as 1,4,5,8,9,12-hexaazatriphenylenehexanitrile; metal complexes; and crosslinkable compounds.

[0278] Examples of the aromatic amine derivatives for HIL or HTL include (but are not limited to) the following general structures:

[0279]

[0280] Ar 1 to Ar 9 each of which is selected from the group consisting of: aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, fluorene, phenanthrene, fluoranthene, pyrene, perylene and azulene; aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units, which are the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group. Ar 1 to Ar 9 each of which may be unsubstituted or may be substituted with general substituents as described above, and any two substituents may be joined or fused into a ring.

[0281] In some embodiments, each Ar 1 to Ar 9 independently contains a moiety selected from the group consisting of:

[0282]

[0283] where k is an integer from 1 to 20; X 101 to X 108 is C or N; Z 101 is C, N, O, or S.

[0284] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0285]

[0286] where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, and the coordinating atoms of Y 101 and Y 102 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be connected to the metal; and k' + k" is the maximum number of ligands that can be connected to the metal.

[0287] In some embodiments, (Y 101 -Y 102 ) is 2-phenylpyridine or a 2-phenylimidazole derivative. In some embodiments, (Y 101 -Y 102 ) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a minimum oxidation potential in solution of less than about 0.6 V compared to the Fc + / Fc couple.

[0288] In some embodiments, the HIL / HTL material is selected from the group consisting of: phthalocyanine and porphyrin compounds, starburst triarylamine, CF x fluorocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acids and silane SAMs, triarylamines or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (such as molybdenum oxide and tungsten oxide), n-type semiconducting organic complexes, metal-organic metal complexes, crosslinkable compounds, polythiophene-based polymers and copolymers, triarylamines, triarylamines containing a spirofluorene core, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolocarbazole, isoindole compounds, and metal carbene complexes.

[0289] c) EBL:

[0290] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking the blocking layer. Additionally, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy compared to one or more emitters closest to the EBL interface. In some embodiments, the compound used in the EBL contains at least one carbazole group and / or at least one arylamine group. In some embodiments, the HOMO level of the compound used in the EBL is shallower than the HOMO levels of one or more of the hosts in the EML. In some embodiments, the compound used in the EBL contains the same molecule or the same functional group as one of the hosts described below.

[0291] d) Additional host:

[0292] The light-emitting layer of the organic EL device of the present disclosure preferably contains at least a light-emitting material as a dopant and a host material. Examples of the host material are not particularly limited, and any metal complex or organic compound can be used as long as the host does not completely quench the emission of the dopant. In some embodiments, the emission layer may contain two hosts: a first host and a second host. In some embodiments, the first host is a hole-transporting host, and the second host is an electron-transporting host. In some embodiments, the first host is a hole-transporting host, and the second host is a bipolar host. In some embodiments, the first host is an electron-transporting host, and the second host is a bipolar host. In some embodiments, the first host and the second host may form an exciplex. In some embodiments, the emission layer may contain a third host. In some embodiments, the third host is selected from the group consisting of: a spacer host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the third host forms an exciplex with one of the first host and the second host or with both the first host and the second host. In some embodiments, the emission layer may contain a fourth host. In some embodiments, the fourth host is selected from the group consisting of: a spacer host (wide-bandgap host), a hole-transporting host, and an electron-transporting host. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host, and the third host, with two of the first host, the second host, and the third host, or with each of the first host, the second host, and the third host. In some embodiments, the LUMO of the electron-transporting host is less than -2.4 eV, less than -2.5 eV, less than -2.6 eV, or less than -2.7 eV. In some embodiments, the HOMO of the hole-transporting host is higher than -5.6 eV, higher than -5.5 eV, higher than -5.4 eV, or higher than -5.35 eV. The HOMO and LUMO values can be measured using solution electrochemistry methods. Solution cyclic voltammetry and differential pulse voltammetry can be performed using a CH Instruments model 6201B potentiostat, using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire are used as the working electrode, counter electrode, and reference electrode, respectively. The electrochemical potential can be measured by measuring the peak potential difference using differential pulse voltammetry with an internal ferrocene-ferrocenium redox couple (Fc / Fc+) as an internal standard.According to the literature ((a) Fink R., Heischkel Y., Thelakkat M., Schmidt H.-W., Chem. Mater. 1998, 10, 3620 - 3625; (b) Pommerehne J., Vestweber H., Guss W., Mahrt R.F., Bassler H., Porsch M., Daub J., J. Adv. Mater. 1995, 7, 551), the corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies can be determined by setting the cationic and anionic redox potentials relative to the ferrocene reference (4.8 eV relative to vacuum).

[0293] In some embodiments, the compounds of the invention described herein can be used as one of the hosts described above, and the compounds described below can be used as one or more other hosts described above.

[0294] Examples of metal complexes used as one or more other hosts preferably have the following general formula:

[0295]

[0296] where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, and the coordinating atoms of Y 103 and Y 104 are independently selected from C, N, O, P, and S; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0297] In some embodiments, the metal complex is:

[0298]

[0299] where (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

[0300] In some embodiments, Met is selected from Ir and Pt. In another embodiment, (Y 103 -Y 104 ) is a carbene ligand.

[0301] In some embodiments, one or more other hosts contain at least one selected from the following groups: a group consisting of aromatic hydrocarbon cyclic compounds such as: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, chrysene, phenanthrene, fluorene, pyrene, perylene, and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borata-naphtho[3,2,1-de]anthracene; and a group consisting of 2 to 10 cyclic structural units, the cyclic structural units being the same type or different types of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option within each group may be unsubstituted or may be substituted with a general substituent as described herein or may be further fused.

[0302] In some embodiments, one or more other hosts comprise at least one selected from the portions consisting of the group consisting of:

[0303]

[0304]

[0305] where k is an integer from 0 to 20 or from 1 to 20. X 101 to X 108 are independently selected from C or N. Z 101 and Z 102 are independently selected from C, N, O, or S.

[0306] In some embodiments, one or more other hosts are selected from the group consisting of: arylcarbazole, metal 8-hydroxyquinolinates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, based on Compounds, aryltriptycene compounds, polycondensed heteroaryl compounds, donor-acceptor type molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indolocarbazole, 5-membered ring electron-deficient heterocycles (e.g., triazole, oxadiazole), tetracene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aryl compounds, aryl benzoyl esters, carbazole linked by non-conjugated groups, aza-carbazole / dibenzofuran / dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

[0307] In some embodiments, the one or more other hosts comprise at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borata naphtho[3,2,1-de]anthracene, azaborinane, oxaborinane, dihydroacridine, dibenzopyran, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenothiazine, phenoxathiin, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boranyl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-borata naphtho[3,2,1-de]anthracene).

[0308] In some embodiments, the one or more other hosts may be selected from the group consisting of the structures in Host Group 1 below:

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315] Wherein:

[0316] Each of J1 to J6 is independently C or N;

[0317] L' is a direct bond or an organic linking group;

[0318] Each Y AA 、Y BB 、Y CC and Y DD is independently selected from the group consisting of: no bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0319] R A ', R B ', R C ', R D ', R E ', R F ' and R G ' each independently represents mono-substitution up to the maximum number of substitutions, or no substitution;

[0320] Each R, R', R A ', R B ', R C ', R D ', R E ', R F ' and R G ' is independently hydrogen or a substituent selected from the group of general substituents defined herein; any two substituents may be joined or fused to form a ring;

[0321] And where possible, each unsubstituted aromatic carbon atom is optionally replaced by N to form a nitrogen-substituted ring.

[0322] In some embodiments, at least one of J1 to J3 is N; in some embodiments, at least two of J1 to J3 are N; in some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD is preferably O, S and SiRR', more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen heterocycle.

[0323] In some embodiments, the host is selected from the group consisting of: EG1-MG1-EG1 to EG53-MG27-EG53 having the formula EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 having the formula EGa-EGc when MGb is absent, where a is an integer from 1 to 53, b is an integer from 1 to 27, and c is an integer from 1 to 53. The structures of EG1 to EG53 are shown below:

[0324]

[0325]

[0326] The structures of MG1 to MG27 are shown below:

[0327]

[0328]

[0329] In the MGb structure shown above, two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are marked with numbers for identification purposes.

[0330] In some embodiments, the host can be any one of its N - hetero - substituted variants, its fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa - MGb - EGc and is selected from the group consisting of h1 to h112 defined in the following host group 2 list, where each of MGb, EGa, and EGc is defined as follows:

[0331]

[0332]

[0333] In the above table, the EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with a numerical prefix that identifies their bonding positions in the MGb structure.

[0334] e) Emitter materials in the EML:

[0335] One or more emitter materials can be used in combination with the compounds or devices of the present disclosure. The emitter material can be emissive or non - emissive in the current devices as described herein. Examples of emitter materials are not particularly limited, and any compound can be used as long as the compound can produce emission in a conventional OLED device. Examples of suitable emitter materials include, but are not limited to, compounds capable of producing emission via phosphorescence, non - delayed fluorescence, delayed fluorescence (especially thermally activated delayed fluorescence, i.e., TADF (also known as E - type delayed fluorescence)), triplet - triplet annihilation, or combinations of these processes.

[0336] f) HBL:

[0337] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons leaving the emissive layer. The presence of such a blocking layer in a device can result in generally higher efficiency and / or longer lifetime compared to a similar device lacking a blocking layer. Additionally, a blocking layer can be used to confine emission to a desired region of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and / or a higher triplet energy compared to one or more of the emitters closest to the HBL interface.

[0338] In some embodiments, the compound used in the HBL contains the same molecule or the same functional group as used in the host described above.

[0339] In some embodiments, the compound used in the HBL comprises at least one of the following moieties selected from the group consisting of:

[0340]

[0341] where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0342] g) ETL:

[0343] The electron transport layer (ETL) can include a material capable of transporting electrons. The electron transport layer can be intrinsic (undoped) or doped. Doping can be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound can be used as long as it is commonly used to transport electrons.

[0344] In some embodiments, the compound used in the ETL contains at least one of the following moieties in the molecule:

[0345] and fullerenes; where k is an integer from 1 to 20, X 101 to X 108 is selected from C or N; Z 101 is selected from the group consisting of C, N, O, and S.

[0346] In some embodiments, the metal complex used in the ETL contains, but is not limited to, the following general formula:

[0347]

[0348] where (O-N) or (N-N) is a bidentate ligand having a metal coordinated to the atoms O, N, or N,N; L 101 is another ligand; and k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0349] In some embodiments, the ETL material is selected from the group consisting of: anthracene-benzimidazole compounds, azatriphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolinates, metal hydroxybenzoquinolinates, bathocuprine compounds, 5-membered ring electron-deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzimidazole), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0350] h) Charge generation layer (CGL)

[0351] In a tandem or stacked OLED, the CGL plays a fundamental role in performance and consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrodes. The 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.

[0352] In any of the compounds disclosed herein, hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in the compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, the percentage of deuteration has its ordinary meaning and includes the percentage of all possible hydrogen and deuterium atoms replaced by deuterium atoms. In some embodiments, deuterium atoms are attached to aromatic rings. In some embodiments, deuterium atoms are attached to saturated carbon atoms, such as alkyl or cycloalkyl carbon atoms. In some other embodiments, deuterium atoms are attached to heteroatoms, such as Si or Ge atoms.

[0353] It should be understood that the various embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the invention. The invention as claimed may thus 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 the various theories as to why the invention works are not intended to be limiting.

[0354] Experimental data

[0355] Example 1: Cmp 1

[0356] Reaction scheme

[0357]

[0358]

[0359] Step 1. In a 1000 mL round-bottom flask, dissolve 9H-3,9'-bicarbazole (10 g, 1 eq, 30.08 mmol) in toluene (200 mL) and bubble nitrogen through it for 10 minutes. Under a nitrogen flow, add lithium bis(trimethylsilyl)amide (6.544 g, 39.11 mL, 1 M in THF, 1.3 eq, 39.11 mmol) via syringe. Stir the reactants at room temperature under a positive nitrogen pressure for 30 minutes. Then, at room temperature, feed 1-bromo-4-chlorodibenz[b,d]furan (12.70 g, 1.5 Eq, 45.12 mmol), allyl palladium(II) chloride (330.2 mg, 0.03 eq, 902.5 μmol), and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (1.273 g, 0.12 eq, 3.610 mmol) into the solution in one portion. Add a reflux condenser with a rubber septum and purge the system with nitrogen at room temperature for several minutes, then stir at 90 °C in a preheated oil bath under a positive nitrogen pressure for 24 hours.

[0360] After cooling to room temperature, the reaction mixture is quenched with 50 mL of water and extracted with three portions of 100 mL of ethyl acetate. The combined organic extracts are filtered through a silica plug and evaporated to give the crude product as a light brown solid. The crude solid is then purified by column chromatography using silica gel and a gradient of 0 - 25% DCM / heptane. The pure eluates of the combined product are concentrated and crystallized to give 11.2 g (70% yield) of 9-(4-chlorodibenz[b,d]furan-1-yl)-9H-3,9'-bicarbazole as a white crystalline solid.

[0361]

[0362] Step 2. In a 500 mL round-bottom flask, 9H-carbazole (2.522 g, 1.2 eq, 15.08 mmol) was dissolved in toluene (70 mL) and bubbled with nitrogen for 10 minutes. Lithium bis(trimethylsilyl)amide (3.155 g, 19 mL, 1 M in THF, 1.5 eq, 19 mmol) was added via syringe and the reactants were stirred for 30 minutes under a nitrogen flow. The solution turned clear brown and then a solid precipitate was observed. Then 9-(4-chlorodibenz[b,d]furan-1-yl)-9H-carbazole (6.7 g, 1 eq, 12.57 mmol), allyl palladium(II) chloride (138 mg, 0.03 Eq, 377.1 μmol), and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (531.7 mg, 0.12 Eq, 1.508 mmol) were fed into the reaction mixture in one portion. A reflux condenser with a rubber septum was added and the system was purged with nitrogen at room temperature for several minutes, then stirred for 24 hours in a preheated oil bath at 120 °C under a positive nitrogen pressure.

[0363] After cooling to room temperature, the reaction mixture was quenched with 50 mL of water and extracted with three portions of 100 mL of ethyl acetate. The combined organic extracts were filtered through a silica plug and evaporated to give the crude product as a light brown solid. The crude solid was then purified by column chromatography using silica gel and a gradient of 0 - 25% DCM / heptane. The pure eluates of the product were combined and concentrated to crystallization to give 6.3 g (65% yield) of Cmp 1 as a white crystalline solid.

[0364] Example 2: Cmp 2

[0365] Reaction Scheme

[0366]

[0367] Step 1. 9H-Carbazole (2.500 g, 1 Eq, 14.95 mmol) was introduced into a 500 mL round-bottom flask and the headspace of the flask was purged with nitrogen for 10 minutes. Then anhydrous toluene (120 mL) was added and the reaction mixture was stirred at room temperature for 10 minutes. A solution of LiHMDS (2.627 g, 15.70 mL, 1.000 molarity, 1.05 Eq, 15.70 mmol) in THF was added dropwise over 15 minutes. The reaction mixture was stirred at room temperature under nitrogen for 30 minutes. After stirring for 30 minutes, 1-bromo-7-chlorodibenzo[b,d]furan (5.051 g, 1.2 Eq, 17.94 mmol), allylchloropalladium(II) dimer (164.1 mg, 0.03 Eq, 448.5 μmol), and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (632.4 mg, 0.12 Eq, 1.794 mmol) were added to the reaction mixture. The flask was equipped with a reflux condenser and the headspace of the flask was purged with nitrogen for 10 minutes. Then the reaction mixture was heated to 90 °C (oil bath temperature) and allowed to stir under nitrogen for 24 hours. The reaction mixture was cooled to room temperature. Water (200 mL) was added and two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 100 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure at 40 °C to give a brown solid. The resulting crude product was dissolved in dichloromethane (100 mL), then purified by column chromatography eluting with dichloromethane and heptane to give 9-(7-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole as a white solid (4.23 g, 76.6% yield).

[0368]

[0369] Step 2. 9H-3,9'-bicarbazole (8.133 g, 1.5 Eq, 24.47 mmol), 9-(7-chlorodibenz[b,d]furan-1-yl)-9H-carbazole (6.000 g, 1 Eq, 16.31 mmol) were introduced into a 500 mL round-bottom flask, and the headspace of the flask was purged with nitrogen for 10 minutes. Then sodium 2-methyl-2-propanolate (3.919 g, 2.5 Eq, 40.78 mmol) was added, followed by anhydrous toluene (110.00 mL). At room temperature, the reaction mixture was stirred under nitrogen for 30 minutes. Palladium(II) allyl chloride dimer (149.2 mg, 0.025 Eq, 407.8 μmol) and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (575.0 mg, 0.1 Eq, 1.631 mmol) were added to the reaction mixture. The flask was equipped with a reflux condenser and the headspace of the flask was purged with nitrogen for 10 minutes. Then the reaction mixture was heated to 110 °C (oil bath temperature) and allowed to stir under nitrogen for 20 hours. The reaction mixture was cooled to room temperature. Water (200 mL) was added, and the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 100 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure at 40 °C to give a brown solid. The resulting crude product was dissolved in dichloromethane (100 mL), then eluted with dichloromethane and heptane and purified by column chromatography to give Cmp2 as a white solid (10.4 g, 93% yield).

[0370] Example 3: Cmp 3

[0371] Reaction scheme

[0372]

[0373] Step 1. Charge a 1 L three-necked round-bottom flask equipped with a thermocouple sleeve, a glass stopper, and a condenser with an xylene solution (394.7 mL) of 8-bromo-1-chlorodibenzo[b,d]furan (15.00 g, 53.28 mmol), 9H-carbazole (9.948 g, 98.51 wt%, 58.61 mmol), tripotassium phosphate (39.58 g, 186.5 mmol), and 1,2-diaminocyclohexane (a mixture of cis and trans, 18.25 g, 19.5 mL, 159.8 mmol). Stir the reaction mixture for 5 minutes, then add copper(I) iodide (30.44 g, 159.8 mmol). Then heat the reactants to 125 °C and stir overnight while venting to the atmosphere without degassing with nitrogen or an inert atmosphere. Cool the reaction mixture to room temperature and pass it through a silica gel plug (130 g), eluting with toluene (1.7 L). Combine the eluates containing the desired product and concentrate under reduced pressure. The residue is then triturated with acetone (140 mL) and sonicated for 10 minutes, then filtered to give 3-(carbazol-9-yl)-5-chloro-9-oxafluorene as a white solid (14.7 g, 75% yield).

[0374]

[0375] Step 2. Evacuate a 500 mL three-necked round-bottom flask equipped with a thermocouple sleeve, a condenser, a vacuum line adapter, and a glass stopper while heating with a heat gun until the internal temperature reaches >100 °C. After reaching the desired temperature, let the flask stand under vacuum while cooling to room temperature. At this point, release the vacuum and replace the vacuum line adapter with a nitrogen inlet to begin filling the flask. Transfer 9-(9-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole (9.000 g, 24.47 mmol), 9H-3,9'-bicarbazole (8.566 g, 99.7 wt%, 25.69 mmol), and sodium 2-methylprop-2-oxide (5.878 g, 61.17 mmol) into the flask along with toluene (122.3 mL). Stir this reaction mixture under nitrogen for 30 minutes. Then quickly add di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (698.6 mg, 1.982 mmol) and allylpalladium(II) chloride (179.1 mg, 489.4 μmol) to the flask and heat the reaction mixture to 108 °C and stir for 3 days. Then cool the reaction mixture to room temperature and wash it with water (150 mL). Then adsorb the organic layer onto diatomaceous earth and elute with toluene and heptane, purify by column chromatography to give Cmp 3 as a white powder (11.62 g, 72% yield).

[0376] Example 4: Cmp 4

[0377] Reaction Scheme

[0378]

[0379] Step 1: In a 500 mL round-bottom flask equipped with a septum and a stir bar, a mixture of 3-iodo-9H-carbazole (40.00 g, 1.00 Eq, 136.5 mmol), pyridinium p-toluenesulfonate (685.9 mg, 0.02 Eq, 2.729 mmol), and 3,4-dihydro-2H-pyran (57.40 g, 5 Eq, 682.3 mmol) in DCM (220.0 mL) was stirred at 50 °C for 2 h and then at room temperature for 15 h. The reaction mixture was diluted with DCM (100 mL), washed with aqueous NaHCO3 (2 × 100 mL), and dried over MgSO4. After filtration, washing with DCM, and concentration under vacuum at 45 °C, a yellow oil was obtained. The crude product was dissolved in dichloromethane and purified by column chromatography eluting with heptane and EtOAc to afford 3-iodo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole as a white solid (50 g, 96% yield).

[0380]

[0381] Step 2. Toluene (600.0 mL) was charged into a 1 L round-bottom flask equipped with a septum and a stir bar, bubbled with nitrogen for 60 min, and then 3-iodo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole (34.74 g, 98% Wt, 1.5 Eq, 90.25 mmol), 9H-3,9'-bicarbazole (20.00 g, 1 Eq, 60.17 mmol), t-BuXPhos (5.110 g, 0.2 Eq, 12.03 mmol), tris(dibenzylideneacetone)dipalladium (5.510 g, 0.1 Eq, 6.017 mmol), and sodium 2-methyl-2-propanolate (16.77 g, 2.9 Eq, 174.5 mmol) were added, and the mixture was stirred at 140 °C under nitrogen for 48 h. The reaction mixture was slowly cooled with stirring to solidify the mixture. The mixture was diluted with EtOAc (1 L) and deionized water (1.2 L), and all solids dissolved. The layers were separated, and the aqueous layer was extracted with EtOAc (3 × 500 mL). The combined organics were dried over MgSO4, then filtered and concentrated under vacuum at 45 °C. The crude compound was purified by column chromatography eluting with heptane and EtOAc to afford 30 g of 9-(tetrahydro-2H-pyran-2-yl)-9H-3,9':3',9”-tricarbazole.

[0382]

[0383] Step 3. In a 500 mL round-bottom flask equipped with a condenser and a stir bar, a suspension of 9-(tetrahydro-2H-pyran-2-yl)-9H-3,9':3',9”-tercarbazole (18.00 g, 1 Eq, 30.94 mmol) and 12 M HCl (11.28 g, 25.79 mL, 12.00 molarity, 10 Eq, 309.4 mmol) in THF (150 mL) was prepared and then heated at 50 °C for 48 h. 10 mL of HCl (12 M) was added to the reaction mixture and the temperature was set at 60 °C for an additional 24 h. The mixture was quenched with aqueous NaHCO3 (50 mL) and DCM (200 mL). It was stirred until most of the vigorous bubbling stopped and then poured into a separatory funnel containing additional aqueous NaHCO3 (50 mL). The phases were shaken and separated; the pH of the aqueous phase was almost neutral. The extraction was repeated twice with dichloromethane (100 mL). The combined organics were dried over MgSO4, filtered and concentrated in vacuo at 45 °C to give a brown oil. The residue was dissolved in dichloromethane and purified by column chromatography eluting with heptane and DCM to give 10 g of the desired compound. This compound was dissolved in 30 mL of THF and slowly poured into 200 mL of methanol and stirred for 2 days. White crystals formed. The crystals were filtered off, washed with HPLC-grade n-hexane (3 × 10 mL) and air-dried to give 10 g of 9H-3,9':3',9”-tercarbazole (64% yield).

[0384]

[0385] Step 4. Add xylene (400.0 mL) and the solid reagents all at once to a 500 mL round-bottom flask equipped with a condenser and a stir bar. The solid reagents include 8-bromo-1-chlorodibenz[b,d]furan (15.00 g, 1 Eq, 53.28 mmol), 9H-carbazole (9.354 g, 1.05 Eq, 55.94 mmol), tripotassium phosphate (39.58 g, 15.44 mL, 3.5 Eq, 186.5 mmol), and (1R,2R)-1,2-cyclohexanediamine (18.25 g, 0.02 L, 3 Eq, 159.8 mmol). Stir the reaction mixture at room temperature for 5 minutes, then add copper(I) iodide (30.44 g, 5.42 mL, 3 Eq, 159.8 mmol), and then heat the mixture to 125 °C and stir overnight while exposed to air. Allow the mixture to cool and partition between DI water (100 mL) and EtOAc (160 mL). After adding some brine, the phases separate slowly. The aqueous phase is additionally extracted with EtOAc (2 × 100 mL), and the combined organic phases are dried over MgSO4 and concentrated under vacuum at 45 °C. Elute with toluene (4 L), and pass the residue through a silica gel plug (130 g). Combine the eluates containing the desired product and concentrate under vacuum at 45 °C to give a yellow oil. Redissolve it in an excess of dichloromethane and purify by column chromatography eluting with heptane and DCM to give 14 g (ca. 70% yield) of 9-(9-chlorodibenz[b,d]furan-2-yl)-9H-carbazole as a white solid.

[0386]

[0387] Step 5: Evacuate a 500 mL three-neck round-bottom flask equipped with a thermocouple well, condenser, vacuum line adapter, and glass stopper, and heat it with a heat gun until the internal temperature reaches >100 °C. After reaching the desired temperature, let the flask stand under vacuum while cooling to room temperature. At this point, release the vacuum and replace the vacuum line adapter with a nitrogen inlet to begin filling the flask. Transfer 9-(9-chlorodibenzo[b,d]furan-2-yl)-9H-carbazole (8.000 g, 1 Eq, 21.75 mmol), 9H-3,9':3',9”-tricarbazole (11.36 g, 1.05 Eq, 22.84 mmol), sodium 2-methylpropan-2-olate (8.360 g, 4 Eq, 87.00 mmol), and toluene (160 mL) into the flask. Stir this reaction mixture under nitrogen for 30 minutes. Then quickly add di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (cBRIDP) (920.0 mg, 0.12 Eq, 2.610 mmol) and allylpalladium(II) chloride (159.2 mg, 0.04 Eq, 870.0 μmol) to the flask and heat the reaction mixture to 110 °C and stir for 24 hours. After 2 hours, the mixture darkens. Then cool the reaction mixture to room temperature and wash it with water (150 mL). Concentrate the organic phase, then elute with DCM and heptane and purify by column chromatography to obtain Cmp 4 as a white powder (10 g, 55% yield).

[0388] Example 5: Cmp 5

[0389] Reaction Scheme

[0390]

[0391]

[0392] Step 1. In a 500 mL round-bottom flask, 9H-carbazole (5.350 g, 1 Eq, 32.00 mmol) was dissolved in toluene (200 mL) and bubbled with nitrogen for 10 minutes. Under a nitrogen flow, lithium bis(trimethylsilyl)amide (7 g, 42 mL, 1 M in THF, 1.3 Eq, 42 mmol) was added via syringe. The reaction mixture was stirred for 30 minutes at room temperature under a positive nitrogen pressure. Then at room temperature, 1-bromo-4-chlorodibenz[b,d]furan (11.71 g, 1.3 Eq, 41.59 mmol), allyl palladium(II) chloride (351.2 mg, 0.03 Eq, 959.9 μmol), and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (1.353 g, 0.12 Eq, 3.839 mmol) were fed into the solution in one portion. A reflux condenser with a rubber septum was added and the system was purged with nitrogen at room temperature for several minutes, then stirred under a positive nitrogen pressure in a preheated oil bath at 90 °C for 24 hours. After cooling to room temperature, the reaction mixture was quenched with 50 mL of water and extracted with three portions of 100 mL of ethyl acetate. The combined organic extracts were filtered through a silica gel plug and evaporated to give the crude product as a light brown solid. The crude solid was then purified by column chromatography using silica gel and a gradient of 0 - 25% DCM / heptane. The pure eluates of the product were combined and concentrated to crystallize, giving 5.39 g (46% yield) of the product as a white crystalline solid.

[0393]

[0394] Step 2. In a 500 mL round-bottom flask, 9H-3,9'-bicarbazole (6.000 g, 1.234 Eq, 18.05 mmol) was dissolved in toluene (98 mL) and bubbled with nitrogen for 10 minutes. Lithium bis(trimethylsilyl)amide (3.7 g, 22 mL, 1 M in THF, 1.5 Eq, 22 mmol) was added via syringe and the reaction mixture was stirred for 30 minutes under a nitrogen flow. The solution turned clear brown and then a solid precipitate was observed. Then 9-(4-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole (5.380 g, 1 Eq, 14.63 mmol), allyl palladium(II) chloride (160.5 mg, 0.03 Eq, 438.8 μmol), and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (618.7 mg, 0.12 Eq, 1.755 mmol) were fed into the reaction mixture all at once. A reflux condenser with a rubber septum was added and the system was purged with nitrogen for several minutes at room temperature and then stirred in a preheated oil bath at 120 °C under a positive nitrogen pressure for 24 hours. After cooling to room temperature, the reaction mixture was quenched with 50 mL of water and extracted with three portions of 100 mL of ethyl acetate. The combined organic extracts were filtered through a silica plug and evaporated to give the crude product as a light brown solid. The crude solid was then purified by column chromatography using silica gel and a gradient of 0 - 25% DCM / heptane. The pure eluates of the product were combined and concentrated to crystallization to give 6.3 g (65% yield) of Cmp 5 as a white crystalline solid.

[0395] Example 6: Cmp 6

[0396] Reaction Scheme

[0397]

[0398] Step 1. 9H-Carbazole (5.000 g, 1 Eq, 29.90 mmol) was introduced into a 1000 mL round-bottom flask and the headspace of the flask was purged with nitrogen for 10 minutes. Then anhydrous toluene (250.0 mL) was added and the reaction mixture was stirred at room temperature for 10 minutes. A solution of lithium bis(trimethylsilyl)amide (5.254 g, 31.40 mL, 1.000 molarity, 1.05 Eq, 31.40 mmol) in toluene was added dropwise over 15 minutes. The reaction mixture was stirred at room temperature under nitrogen for 30 minutes. After stirring for 30 minutes, 1-bromo-7-chlorodibenzothiophene (10.68 g, 1.2 Eq, 35.88 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (1.265 g, 0.12 Eq, 3.588 mmol) and allyl(palladium(II) chloride (437.6 mg, 0.04 Eq, 1.196 mmol) were added to the reaction mixture. The flask was equipped with a reflux condenser and the headspace of the flask was purged with nitrogen for 10 minutes. Then the reaction mixture was heated to 90 °C and stirred under nitrogen for 24 hours. The reaction mixture was cooled to room temperature, water (200 mL) and ethyl acetate (200 mL) were added, and the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 200 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure at 50 °C to give a brown solid. The resulting crude product was dissolved in dichloromethane and then purified by column chromatography eluting with heptane and dichloromethane to afford the compound 9-(7-chlorodibenzothiophen-1-yl)-9H-carbazole as a white foam solid (7.0 g, 61% yield).

[0399]

[0400] Step 2. 9-(7-Chlorodibenzothiophen-1-yl)-9H-carbazole (1.000 g, 1 Eq, 2.605 mmol) and 9H-3,9'-bicarbazole (1.299 g, 1.5 Eq, 3.907 mmol) were introduced into a 250 mL round-bottom flask and the headspace of the flask was purged with nitrogen for 5 minutes. Then NaO tBu (751.0 mg, 3.0 Eq, 7.815 mmol) was added, followed by anhydrous toluene (110.00 mL). The reaction mixture was stirred for 10 minutes at room temperature under nitrogen. Allyl palladium(II) chloride (38.12 mg, 0.04 Eq, 104.2 μmol) and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (110.2 mg, 0.12 Eq, 312.6 μmol) were added to the reaction mixture. The flask was equipped with a reflux condenser and the headspace of the flask was purged with nitrogen for 10 minutes. Then the reaction mixture was heated to 110 °C and stirred for 20 hours under nitrogen. The reaction mixture was cooled to room temperature, water (50 mL) and ethyl acetate (50 mL) were added, and the two layers were separated. The aqueous layer was extracted with ethyl acetate (3 × 50 mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure at 50 °C to give a brown solid. The resulting crude product was dissolved in dichloromethane and then purified by column chromatography eluting with heptane and dichloromethane to afford 1.1 g of white solid product Cmp 6 (1.1 g, 62% yield).

[0401] Example 7: Cmp 7

[0402] Reaction Scheme

[0403]

[0404] Step 1. Toluene (1.921 L) and tripotassium phosphate (126.7 g, 3 Eq, 596.7 mmol) were added to a round-bottom flask. Then 0.5 L of toluene was distilled off to ensure that all H2O was removed. Then 1-bromo-8-chlorodibenzo[b,d]furan (56.00 g, 198.9 mmol), 9H-carbazole (36.59 g, 218.8 mmol), cyclohexane-1,2-diamine (68.14 g, 72.7 mL, 596.7 mmol) and CuI (75.77 g, 397.8 mmol) were added to the flask. Then the reaction mixture was refluxed and stirred for one week while exposed to air. The reaction mixture was cooled to room temperature and eluted with DCM and filtered through silica gel (200 g). All the eluates containing the product were combined and concentrated. The resulting residue was then adsorbed onto silica gel (50 g), added to a silica column (200 g) and eluted with a gradient of 0 - 15% DCM / heptane, with most of the product eluting in 15% DCM / heptane. The pure eluates were combined, concentrated and left overnight under high vacuum to give 9-(8-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole as a white solid (5.91 g, 8%).

[0405]

[0406] Step 2. Add 9-(8-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole (5.910 g, 16.07 mmol), 9H-3,9'-bicarbazole (5.875 g, 17.67 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (659.6 mg, 1.607 mmol), xylene (80.34 mL), and sodium tert-butoxide (3.860 g, 40.17 mmol) to a round-bottom flask purged with N2. The reaction mixture was purged with N2 for 10 minutes, followed by the addition of Pd2(dba)3 (735.7 mg, 803.4 μmol). The mixture was purged with N2 again for 10 minutes, and then stirred overnight at 135 °C. Then the reaction mixture was cooled to room temperature and eluted with DCM, filtered through a silica gel plug (20 g). All the eluates containing the desired product were combined, concentrated and adsorbed onto silica gel (10 g). Then it was added onto a silica gel column (400 g) and the product was eluted with a gradient of 0 - 35% DCM / heptane. The pure eluate was concentrated and placed under high vacuum overnight. Then the white solid was triturated in heptane (50 mL) and sonicated for 10 minutes, followed by filtration and placed under high vacuum overnight. Thereby, white solid Cmp 7 (6.24 g, 59%) was obtained.

[0407] Example 8: Cmp 8

[0408] Reaction Scheme

[0409]

[0410] Step 1. Add 8-bromo-1-chlorodibenz[b,d]furan (6.000 g, 1 Eq, 21.31 mmol), 9H-3,9'-bicarbazole (21.25 g, 3 Eq, 63.94 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (2.254 g, 0.3 Eq, 6.394 mmol), sodium 2-methylpropan-2-olate (8.192 g, 4 Eq, 85.25 mmol) and toluene (200.0 mL) to a 500 mL round-bottom flask. The reaction mixture is bubbled with nitrogen for 10 minutes. Then add allyl palladium(II) chloride (779.8 mg, 0.1 Eq, 2.131 mmol) and continue bubbling for an additional 10 minutes. The reaction mixture is continuously stirred in an oil bath overnight. The reaction mixture is cooled to room temperature, water (100 mL) and ethyl acetate (200 mL) are added to the reaction mixture to form a precipitate. The suspension is filtered, and the precipitate is dissolved in hot tetrahydrofuran (200 mL) and filtered through a pad of diatomaceous earth. The solvent is removed in vacuo at 50 °C on a rotary evaporator. The crude product is dissolved in dichloromethane and then purified by column chromatography eluting with heptane and dichloromethane to give white solid Cmp 8 (8.3 g, 47% yield).

[0411] Example 9: Cmp 9

[0412] Reaction Scheme

[0413]

[0414] Step 1. Introduce 9H-carbazole (3.140 g, 18.78 mmol), 1-bromo-6-chlorodibenz[b,d]furan (5.28 g, 18.78 mmol) and anhydrous toluene (100 mL) into a 250 mL dry round-bottom flask. Then, at room temperature, a solution of lithium bis(trimethylsilyl)amide (19.80 mL, 1.000 molarity, 19.72 mmol) is added dropwise over 10 minutes and the mixture is stirred for 30 minutes. Di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (877 mg, 2.49 mmol) and allyl palladium(II) chloride dimer (364 mg, 995 μmol) are added in one portion. The headspace of the flask is purged with nitrogen for 10 minutes. A freshly prepared N2 balloon is attached and the mixture is stirred at 90 °C for 3 hours. The reaction mixture is cooled to room temperature and 100 mL of EtOAc and 100 mL of water are added. The layers are separated and the aqueous layer is extracted with EtOAc (2 × 80 mL). The organic layers are combined, dried over anhydrous MgSO4, filtered, and concentrated in vacuo at 48 °C to give a dark brown solid. This brown solid is purified by SiO2 column chromatography (eluent: 5 to 20% DCM / heptane) to give the product as a white solid (5.5 g, 79% yield).

[0415]

[0416] Step 2. Introduce 9-(6-chlorodibenzo[b,d]furan-1-yl)-9H-carbazole (5.50 g, 14.95 mmol) and xylene (200 mL) into a 500 mL dry round-bottom flask. Then, add 9H-3,9'-bicarbazole (6.5 g, 19.44 mmol), NaOtBu (3.60 g, 37.38 mmol), di-tert-butyl(2',4',6'-triisopropyl-[1,1'-biphenyl]-2-yl)phosphine (762 mg, 1.79 mmol), and Pd2(dba)3 (684.63 mg, 747.63 μmol) in one portion. Purge the headspace of the flask with nitrogen for 10 minutes. Attach a freshly prepared N2 balloon and stir the mixture at 135 °C (preheated oil bath) for 16 hours. Cool the reaction mixture to room temperature and add 100 mL of water and 100 mL of EtOAc. Separate the layers and extract the aqueous layer with EtOAc (2 × 80 mL). Combine the organic layers, dry over anhydrous MgSO4, filter, and concentrate under vacuum at 48 °C to give a dark brown solid. Purify this brown solid by SiO2 column chromatography (eluent: 0 to 100% DCM / heptane) to give Cmp 9 as a white solid (5.52 g, 56% yield).

[0417] Example 10: Cmp 10

[0418] Reaction Scheme

[0419]

[0420] Step 1. Add 8-bromo-1-chlorodibenzo[b,d]thiophene (2.000 g, 1 Eq, 6.721 mmol), 9H-3,9'-bicarbazole (6.702 g, 3 Eq, 20.16 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (710.7 mg, 0.3 Eq, 2.016 mmol), sodium 2-methylpropan-2-olate (2.583 g, 4 Eq, 26.88 mmol) and toluene (60.00 mL) into a 250 mL round-bottom flask and bubble the reaction mixture with nitrogen for 10 minutes. Then add allylpalladium(II) chloride (245.9 mg, 0.1 Eq, 672.1 μmol) and continue bubbling for another 10 minutes. Heat the reaction mixture to 100 °C in an oil bath and stir overnight. Cool the reaction mixture to room temperature, add water (100 mL) and ethyl acetate (100 mL) to the reaction mixture. Filter the solution and dissolve the undissolved solid in hot chloroform (400 mL) and filter through diatomaceous earth. On a rotary evaporator, remove the solvent under vacuum at 50 °C to obtain a grayish-white solid product Cmp 10 (3.6 g, 63.4% yield).

[0421] Example 11: Cmp 11

[0422] Reaction process

[0423]

[0424] Reaction process

[0425] At room temperature, 9H-3,9'-bicarbazole-1,1',2,2',3',4,4',5,5',6,6',7,7',8,8'-d 15(65.3 g, 187.8 mmol, 3.0 equiv) was added to a suspension of sodium tert-butoxide (24.0 g, 250.4 mmol, 4.0 equiv) in anhydrous xylene (360 mL). After stirring for 5 minutes, 2,8-dibromodibenzo[b,d]furan-1,3,4,6,7,9-d6 (18.0 g, 62.6 mmol, 1.0 equiv) was added while bubbling with nitrogen, followed by di-tert-butyl(1,1-diphenylprop-1-en-2-yl)phosphine (6.4 g, 18.8 mmol, 0.3 equiv) and allylpalladium(II) chloride dimer (2.3 g, 6.3 mmol, 0.1 equiv). After heating at 135 °C for one weekend, the reaction mixture was cooled to room temperature and diluted with dichloromethane (1.2 L) and water (150 mL). The layers were separated, and the organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified on silica gel using dichloromethane / hexane to give 9,9''-(dibenzo[b,d]furan-1,8-diyl-d6)bis((9H-3,9'-bicarbazole-1,1',2,2',3',4,4',5,5',6,6',7,7',8,8'-d 15 )) Cmp 11 (9.9 g, 16% yield).

[0426] The HOMO and LUMO values of compounds H1 to H11 were determined using solution electrochemistry. Cyclic voltammetry and differential pulse voltammetry were performed using a CH Instruments Model 6201B potentiostat, an anhydrous dimethylformamide solvent, and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. A glassy carbon, platinum, and silver wire were used as the working, counter, and reference electrodes, respectively. The electrochemical potential was measured by taking the peak potential difference using differential pulse voltammetry with the internal ferrocene-ferrocenium redox couple (Fc / Fc+) as the internal standard. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were determined by referencing the cationic and anionic redox potentials to the ferrocene reference (4.8 eV versus vacuum) according to the literature ((a) Fink R.; Heischkel Y.; Thelakkat M.; Schmidt H.-W., Chem. Mater. 1998, 10, 3620 - 3625; (b) Pommerehne J.; Vestweber H.; Guss W.; Mahrt R.F.; Bassler H.; Porsch M.; Daub J., J. Adv. Mater. 1995, 7, 551).

[0427] The triplet energies of compounds H1 to H11 were measured and are shown in Table 1. T1 was obtained from the highest energy peak of the gated emission of the frozen sample in 2-MeTHF at 77 K. The gated emission spectra were collected on a Horiba Fluorolog-3 spectrofluorometer equipped with a xenon flash lamp (flash delay of 10 milliseconds and collection window of 50 milliseconds). All samples were excited at 300 nm.

[0428] Table 1: Electrochemical and Photophysical Properties of Selected Compounds

[0429] Compound T1 (nm) HOMO (eV) LUMO (eV) Compound H1 430 -5.58 -2.13 Compound H2 432 -5.54 -2.16 Compound H3 417 -5.54 -2.15 Compound H4 417 -5.49 -2.15 Compound H5 423 -5.56 -2.15 Compound H6 434 -5.54 -2.14 Compound H7 418 -5.53 -2.14 Compound H8 416 -5.53 -2.16 Compound H9 416 -5.55 -2.14 Compound H10 412 -5.53 -2.17 Compound H11 416 -5.53 -2.14

[0430] As shown in Table 1, the various compounds of the present invention exhibit moderately shallow HOMOs sufficient to achieve efficient hole transport properties and high T1 energies that support blue and green triplet energies.

[0431] OLED devices were fabricated using the H host of the present invention and Comparative Example C1 as the hole transport host. The device results are shown in Table 2, where the relative LT90 is reported at 1000 nits (nits).

[0432]

[0433]

[0434] The OLED is grown on a glass substrate pre-coated with an indium tin oxide (ITO) layer having a sheet resistance of 15 - Ω / sq. Before any organic layer is deposited or coated, the substrate is degreased with a solvent and then treated with oxygen plasma at 100 mTorr and 50 W for 1.5 minutes and with UV ozone for 5 minutes. The device is fabricated by thermal evaporation in a high vacuum (<10 -6 Torr). The anode electrode is indium tin oxide (ITO). After all the devices are fabricated, they are immediately encapsulated with a glass lid in a nitrogen glove box (H2O and O2 < 1 ppm) and sealed with an epoxy resin, with a desiccant incorporated inside the encapsulation. The doping percentages are in volume percentages.

[0435] The devices shown in Table 2 have an organic layer consisting of the following in sequence: from the ITO surface, Compound 1 (HIL), Compound 2 (HTL), a selected H host (EBL), an H host (EML) doped with 35% E host and 12% emitter 1, the E host (BL), Compound 3 (ETL) doped with 35% Compound 4, Compound 3 (EIL), followed by Al (cathode), where the H hosts are shown in Table 2. The lifetime of the device examples is reported relative to the values of Comparative Example 1.

[0436] Table 2: Device Performance

[0437] H Host CIE λmax (nm) LT90 at 1 K cd / m² Example 1 Compound H2 (0.137,0.154) 461 154％ Example 2 Compound H3 (0.136,0.146) 461 188％ Example 3 Compound H7 (0.136,0.155) 461 188％ Comparative Example 1 Compound C1 (0.136,0.142) 460 100％

[0438] The above data show that each of Device Examples 1 to 3, which includes a compound of the present invention as a hole - transporting host (H host), exhibits a longer lifetime than the comparative devices using related analogs in Comparative Example C1. The lifetimes of Examples 1 to 3 are extended by 54 to 88% over any value attributable to experimental error, and the observed improvement is significant. Based on the fact that the devices have the same device structure and the only difference lies in the substitution on dibenzofuran (DBF) in the hole - transporting host, the significant performance improvement observed from the above data is unexpected. Without being limited by any theory, this improvement can be attributed to the additional substitution on the DBF core, where the additional carbazole unit can potentially block the reactive sites on DBF.

Claims

1. A compound comprising a structure of Formula I: where Y A is selected from the group consisting of O, S and Se; wherein X 1 to X 7 are each independently C or N; wherein R A and R B each independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution; wherein R A and R B are each independently hydrogen or selected from the group consisting of deuterium, fully or partially deuterated substituents, and substituted or unsubstituted carbazoles, provided that neither R A nor R B is a substituted or unsubstituted C6-C 12 aryl; wherein R 1 is a substituted or unsubstituted carbazole, or a substituted or unsubstituted azacarbazole; wherein the compound comprises at least three carbazole or azacarbazole moieties, and wherein at least two carbazole or azacarbazole moieties are joined to form a group selected from: 1,9-bicarbazole, 2,9-bicarbazole, 3,9-bicarbazole, and 4,9-bicarbazole and their aza-variants; wherein any two substituents may be joined or fused to form a ring; with the proviso that none of the carbazole moieties is joined to a ring group other than ring B via a C-C bond; and wherein the compound is not:

2. The compound according to claim 1, wherein Y A is O; and / or wherein X 1 to X 7 are all C.

3. The compound according to claim 1, wherein at least one carbazole moiety is attached to ring A; and / or wherein at least one carbazole moiety is attached to X 1 ; and / or wherein at least one carbazole moiety is attached to X 3 .

4. The compound according to claim 1, wherein at least two carbazole moieties are joined to form 3,9-bicarbazole.

5. The compound according to claim 1, wherein the compound comprises exactly three carbazole groups; or wherein the compound comprises exactly four carbazole groups.

6. The compound according to claim 1, wherein R 1 is a substituted or unsubstituted tricarbazole group; or wherein R 1 is a substituted or unsubstituted bicarbazole group and at least one of R A and R B is a substituted or unsubstituted carbazole.

7. The compound according to claim 1, wherein at least one R A is a fully or partially deuterated substituent.

8. The compound according to claim 1, wherein one of R A and R B is a substituted or unsubstituted carbazole group and the remaining sites are all deuterium.

9. The compound according to claim 1, wherein the compound is selected from the group consisting of: wherein X 8 to X 31 are each independently C or N; wherein R C , R D , R E , R F , R G , R H and R I independently represent mono-substitution to the maximum allowable number of substitutions or unsubstituted; where each R C , R D , R E , R F , R G , R H and R I is independently hydrogen or selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boranyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenyl and combinations thereof.

10. The compound according to claim 1, wherein the compound is selected from the group consisting of: compound W1-(Ai)(Bj)(Yk), compound W2-(Ai)(Bj)(Rl)(Yk), where W1 is an integer from 1 to 12, W2 is an integer from 13 to 42, each i is an integer from 1 to 24, each j is an integer from 1 to 15, each l is an integer from 1 to 45 and each k is an integer from 1 to 3, each Ai is independently selected from the group consisting of A1 to A24, each Bj is independently selected from the group consisting of B1 to B15, each Rl is independently selected from the group consisting of R1 to R45, each Yk is independently selected from the group consisting of Y1 to Y3, and each of compound 1-(A1)(B1)(Y1) to compound 12-(A24)(B15)(Y3) and compound 13-(A1)(B1)(R1)(Y1) to compound 42-(A24)(B15)(R45)(Y3) is defined in the following table: where Y1 is O, Y2 is S and Y3 is Se, and wherein A1 to A24 have the following structures: wherein B1 to B15 have the following structures: wherein R1 to R45 have the following structures:

11. The compound according to claim 1, wherein the compound is selected from the group consisting of the structures in List 1 as defined herein.

12. An organic light-emitting device OLED comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound having a structure of Formula I: wherein Y A is selected from the group consisting of O, S and Se; wherein X 1 to X 7 are each independently C or N; wherein R A and R B each independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution; wherein R A and R B are each independently hydrogen or selected from the group consisting of deuterium, fully or partially deuterated substituents, and substituted or unsubstituted carbazoles, provided that neither R A nor R B is a substituted or unsubstituted C6-C 12 aryl; wherein R 1 is a substituted or unsubstituted carbazole, or a substituted or unsubstituted azacarbazole; wherein said compound comprises at least three carbazole or azacarbazole moieties, and wherein at least two of the carbazole or azacarbazole moieties are joined to form a group selected from: 1,9-bicarbazole, 2,9-bicarbazole, 3,9-bicarbazole, and 4,9-bicarbazole and their aza-variants; wherein any two substituents may be joined or fused to form a ring; with the proviso that none of the carbazole moieties is joined via a C-C bond to a ring group other than ring B; and wherein said compound is not:

13. The OLED according to claim 12, wherein the compound is a host, and the organic layer is an emission layer containing a phosphorescent material, and wherein the phosphorescent material is a metal coordination complex having the formula M(L 1 ) x (L 2 ) y (L 3 ) z ; where L 1 , L 2 and L 3 may be the same or different; wherein x is 1, 2, or 3; wherein y is 0, 1, or 2; wherein z is 0, 1, or 2; wherein x + y + z is the oxidation state of the metal M; where L 1 is selected from the group consisting of the structures in the following ligand list: wherein L 2 and L 3 are independently selected from the group consisting of: and the structures in the ligand list; wherein: T is selected from the group consisting of B, Al, Ga, and In; K 1 ' is a direct bond or is selected from the group consisting of NR e , PR e , O, S and Se; Each Y 1 to Y 13 is independently selected from the group consisting of carbon and nitrogen; Y' is selected from the group consisting of: 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 ; R e With R f can be fused or joined to form a ring; Each R a , R b , R c and R d may independently represent mono-substitution to the maximum possible number of substitutions, or no substitution; Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f is independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boranyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenyl and combinations thereof; and Wherein R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two of them may be fused or joined to form a ring or form a polydentate ligand.

14. The OLED according to claim 12, wherein said compound is a host and said OLED comprises a receptor as an emitter and a sensitizer selected from the group consisting of delayed fluorescence materials, phosphorescent materials, and combinations thereof; wherein the sensitizer transfers energy to the receptor.

15. A consumer product comprising an organic light-emitting device (OLED), said organic light-emitting device comprising: an anode; a cathode; and an organic layer disposed between said anode and said cathode, wherein said organic layer comprises a compound having a structure of Formula I: where Y A is selected from the group consisting of O, S, and Se; wherein X 1 to X 7 is each independently C or N; wherein R A and R B each independently represents mono-substitution to the maximum allowable number of substitutions, or no substitution; wherein R A and R B are each independently hydrogen or selected from the group consisting of deuterium, fully or partially deuterated substituents, and substituted or unsubstituted carbazole, with the proviso that neither R A nor R B is a substituted or unsubstituted C6-C 12 aryl; wherein R 1 is a substituted or unsubstituted carbazole, or a substituted or unsubstituted azacarbazole; wherein said compound comprises at least three carbazole or azacarbazole moieties, and wherein at least two of the carbazole or azacarbazole moieties are joined to form a group selected from: 1,9-bicarbazole, 2,9-bicarbazole, 3,9-bicarbazole, and 4,9-bicarbazole and their aza-variants; wherein any two substituents may be joined or fused to form a ring; with the proviso that none of the carbazole moieties is joined via a C-C bond to a ring group other than ring B; and wherein said compound is not:

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