Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. Providing a compound of formula R1R2R3M-L-M '; wherein M is Si or Ge; l is selected from the group consisting of direct bonds or from the group consisting of O, S, Se, BR, BRR ', PR, CR, NR, C = O, C = S, C = NR, C = CRR', CRR ', SO, SO2, SiRR', GeRR ', and P (O) R; when L is a direct bond, M'is SiR < 4 > R < 5 > R < 6 > or GeR < 4 > R < 5 > R < 6 >; and when L is not a direct bond, M'is SiR4R5R6, GeR4R5R6, or one or more hydrocarbyl groups, with the proviso that at least one of the one or more hydrocarbyl groups is a carbocyclic group. Formulations comprising these compounds are also provided. Further provided are organic light emitting devices (OLEDs) and related consumer products utilizing these compounds.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is a continuation-in-part of U.S. patent application No. 18 / 482,916 filed on October 9, 2023, which claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 382,116 filed on November 3, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates generally to organic or metal coordination compounds and formulations and various uses thereof, 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] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many materials used to manufacture the devices are relatively inexpensive, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can make them more suitable for specific applications, such as manufacturing 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 across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as displays, lighting, and backlighting.

[0006] One application of emissive molecules is full-color displays. Industry standards for such displays require pixels adapted to emit specific colors, called "saturated" colors. Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, an absorption filter is used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates, which are well known in the art. Summary of the invention

[0007] In one aspect, the present disclosure provides a formula R 1 R 2 R 3 ML-M' compounds;

[0008] in

[0009] M is Si or Ge;

[0010] L is selected from the group consisting of direct bonds or from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO 2 , SiRR', GeRR' and P(O)R;

[0011] When L is a direct bond, M' is SiR 4 R 5 R 6 or GeR 4 R 5 R 6 ;

[0012] When L is not a direct bond, M' is SiR 4 R 5 R 6 ,GeR 4 R 5 R 6 or one or more hydrocarbon groups, provided that at least one of the one or more hydrocarbon groups is a carbocyclic group;

[0013] Each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0014] Any two substituents may be joined or fused to form a ring.

[0015] In another aspect, the present disclosure provides a formulation of a compound described herein.

[0016] In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound described herein.

[0017] In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising the compound described herein. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0019] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated. DETAILED DESCRIPTION

[0020] A. Terminology

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

[0022] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed "above" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, there may be other layers between the first and second layers. For example, a cathode may be described as being "disposed "above" an anode even though various organic layers are present between the cathode and the anode.

[0023] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0024] As used herein, and as will be generally understood by one skilled in the art, a 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 if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy 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 with the vacuum energy level at the top, 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.

[0025] As used herein, and as one skilled in the art would generally understand, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are typically measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows different rules than work functions.

[0026] Layers, materials, regions, and devices may be described herein with reference to the color of light they emit. Generally, as used herein, an emissive region described as producing a particular color of light may include one or more emissive layers disposed on top of each other in a stacked fashion.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] In some cases, it may be preferred to describe the color of a component, such as the color of an emitting region, a sub-pixel, a color-changing layer, etc., in terms of 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one in or near the edge of a "green" region, and one in or near the edge of a "red" region, as previously described. Thus, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. Shapes in the 1931 CIE color space are constructed by tracing the trajectory between two color points and any other interior points. For example, the interior shape parameters for red, green, blue, and yellow may be defined as follows:

[0031]

[0032] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0033] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0034] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0035] The term "ether" refers to -OR s Group.

[0036] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0037] The term "selenoalkyl" refers to -SeR s Group.

[0038] The term "sulfinyl" refers to -S(O)-R s Group.

[0039] The term "sulfonyl" refers to -SO2 -R s Group.

[0040] The term "phosphino" refers to a group containing at least one phosphorus atom bonded to a related structure. Common examples of phosphino groups include, but are not limited to, -P(R s ) 2 Group or -PO(R s ) 2 A group of groups, where each R s Can be the same or different.

[0041] The term "silyl group" refers to a group containing at least one silicon atom bonded to the structure of interest. Common examples of silyl groups include, but are not limited to, -Si(R s ) 3 A group of groups, where each R s Can be the same or different.

[0042] The term "germanyl" refers to a group containing at least one germanium atom bonded to an associated structure. Common examples of germanyl groups include, but are not limited to, -Ge(R s ) 3 A group of groups, where each R s Can be the same or different.

[0043] The term "boryl" refers to a group containing at least one boron atom bonded to the structure of interest. Common examples of boryl groups include, but are not limited to, -B(R s ) 2 Group or its Lewis adduct -B(R s ) 3 A group of groups, where R s Can be the same or different.

[0044] In each of the above, R s It may be hydrogen or a substituent selected from the group consisting of general substituents defined in this application. s is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0045] The term "alkyl" refers to and includes straight and branched chain alkyl groups having alkyl carbon atoms bonded to the relevant structure. Preferred alkyl groups are those containing one to fifteen carbon atoms, preferably one to nine carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. In addition, the alkyl group may be further substituted.

[0046] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups having cycloalkyl carbon atoms bonded to the relevant structure. Preferred cycloalkyl groups are cycloalkyl groups containing 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. In addition, the cycloalkyl group may be further substituted.

[0047] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. In addition, the heteroalkyl or heterocycloalkyl group may be further substituted.

[0048] The term "alkenyl" refers to and includes straight and branched alkenyls.Alkenyl is essentially an alkyl group including at least one carbon-carbon double bond in the alkyl chain, wherein one carbon atom from the carbon-carbon double bond is bonded to a related structure.Cycloalkenyl is essentially a cycloalkyl group including at least one carbon-carbon double bond in a cycloalkyl ring.As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom.Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge and Se, preferably O, S or N.Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those containing two to fifteen carbon atoms.In addition, alkenyl, cycloalkenyl or heteroalkenyl groups may be further substituted.

[0049] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. Alkyl groups are generally alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain, wherein one carbon atom from the carbon-carbon triple bond is bonded to the associated structure. Preferred alkynyl groups are alkynyl groups containing two to fifteen carbon atoms. In addition, alkynyl groups may be further substituted.

[0050] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group having an alkyl carbon atom bonded to the associated structure that is substituted with an aryl group. Additionally, the aralkyl group may be further substituted.

[0051] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge and Se, preferably O, S, N or B. Aromatic heterocyclic groups can be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 10 ring atoms, preferably 3 to 7 ring atoms, including at least one heteroatom, and include cyclic amines, such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, the heterocyclic group can be further substituted or fused.

[0052] The term "aryl" refers to and includes monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclic rings may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"). Preferred aryl groups are those 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 carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene and naphthalene. In addition, the aryl group may be further substituted or fused, such as but not limited to, fluorene.

[0053] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include 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. Monocyclic heteroaromatic systems are preferably monocyclic rings with 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more aromatic rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on 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 heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indole, oxazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenobenzodipyridine, azaborane, borazine, 5λ 2 ,9λ 2 -diaza-13b-boronaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ 2 ,9λ 2 -diaza-13b-boronaphtho[2,3,4-de]anthracene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene. In addition, the heteroaryl group may be further substituted or fused.

[0054] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ 2 ,9λ 2-diaza-13b-boronaphtho[2,3,4-de]anthracene, 5λ 2 -Benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, and their respective aza analogs are of particular interest.

[0055] In many cases, the general substituent is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0056] In some cases, preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0057] In some cases, more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0058] In other cases, even more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silane, aryl, heteroaryl, nitrile, and combinations thereof.

[0059] In other cases, the most preferred general substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0060] The terms "substituted" and "substituted" refer to the bonding of substituents other than H to the relevant positions, such as carbon or nitrogen. For example, when R 1 When it represents a single substitution, one R 1 must not be H (i.e., substituted). Similarly, when R 1 When it indicates disubstituted, the two R 1 must not be H. Similarly, when R 1 When it indicates zero or no substitution, R 1 For example, it can be hydrogen with all available valences of the ring atoms, such as the carbon atoms of benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atoms.

[0061] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents; and halogen, alkyl and aryl can be combined to form haloaralkyl. In one example, the term substitution includes a combination of two to four listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0062] The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in the corresponding aromatic ring can be replaced by a nitrogen atom, for example and without any limitation, azatriphenylene 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.

[0063] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be easily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951 and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entirety) respectively describe the deuteration of methylene hydrogen in benzylamine and the effective way to replace aromatic ring hydrogen with deuterium.

[0064] As used herein, any specific 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 a valence fully filled by H or D should be considered to include their non-deuterated, partially deuterated, and fully deuterated forms. For example, the chemical structure Meaning includes C 6 H 6 , C 6 D 6 , C 6 H 3 D 3 and any other partially deuterated variants thereof. Some common basic partially or fully deuterated groups include, but are not limited to, CD 3 , CD 2 C(CH 3 ) 3 、C(CD 3 ) 3 and C 6 D 5 .

[0065] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another part, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0066] In some cases, a pair of substituents in a molecule can be optionally joined or fused to form a ring. Preferred rings are five to nine-membered carbocyclic or heterocyclic rings, including two cases in which a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. In other cases, a pair of adjacent substituents can be optionally 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 adjacent rings with two closest available substitutable positions (such as 2, 2' positions in biphenyl or 1, 8 positions in naphthalene).

[0067] B. Compounds of the Disclosure

[0068] In one aspect, the present disclosure provides a formula R 1 R 2 R 3 ML-M' compounds;

[0069] in

[0070] M is Si or Ge;

[0071] L is selected from the group consisting of direct bonds or from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO 2 , SiRR', GeRR' and P(O)R;

[0072] When L is a direct bond, M' is SiR 4 R 5 R 6 or GeR 4 R 5 R 6 ;

[0073] When L is not a direct bond, M' is SiR 4 R 5 R 6 ,GeR 4 R 5 R 6 or one or more hydrocarbon groups, provided that at least one of the one or more hydrocarbon groups is a carbocyclic group;

[0074] Each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0075] Any two substituents may be joined or fused to form a ring.

[0076] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, silane, fluorine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, and aza variants thereof.

[0077] In some embodiments, each of R, R', R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0078] In some embodiments, if L is a direct bond, and both M and M' comprise Si, then R 1 , R 2 and R 3 At least one of the following comprises benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim) or borane, or R 1 , R 2 and R 3 together comprising two structures selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, and aza variants thereof, with the additional proviso that R is the same 1 , R 2 and R 3 Contains no dicarbazole.

[0079] In some embodiments, if M is Si, then R 1 , R 2 and R 3 At least two of the are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted.

[0080] In some embodiments, if M' is SiR 4 R 5 R 6 , then R 4 , R 5 and R 6 At least two of the are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted.

[0081] In some embodiments, the compounds contain no non-ring N atoms.

[0082] In some embodiments, the compound comprises at least one electron donating group. In some embodiments, the compound comprises at least one electron withdrawing group. In some embodiments, the compound comprises at least one electron donating group and at least one electron withdrawing group. In some embodiments, R 1 , R 2 and R 3 At least one of the R 4 , R 5 and R 6 At least one of the molecules comprises at least one electron withdrawing group.

[0083] In some embodiments, M is Si.

[0084] In some embodiments, M is Ge.

[0085] In some embodiments, M' is SiR 4 R 5 R 6 .

[0086] In some embodiments, M' is GeR 4 R 5 R 6 .

[0087] In some embodiments, M' is one or more hydrocarbyl groups.

[0088] In some embodiments, M is Si and M' is SiR 4 R 5 R 6 .

[0089] In some embodiments, L is a direct bond.

[0090] In some embodiments, L is O.

[0091] In some embodiments, L is S.

[0092] In some embodiments, L is Se.

[0093] In some embodiments, R 1 -R 3 At least two of the radicals contain phenyl.

[0094] In some embodiments, R 1 -R 3 At least two of them are unsubstituted phenyl groups.

[0095] In some embodiments, R 1 -R 6 At least four of the above mentioned radicals contain phenyl groups.

[0096] In some embodiments, R 1 -R 6 At least four of them are unsubstituted phenyl groups.

[0097] In some embodiments, R 1 -R 6 At least five of the above mentioned radicals contain phenyl.

[0098] In some embodiments, R 1 -R 6 At least five of the groups are unsubstituted phenyl groups.

[0099] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim).

[0100] In some embodiments, R 1 , R 2 and R 3 At least two carbazoles are contained together.

[0101] In some embodiments, R 1 , R 2 and R 3 At least one of the structures comprises a structure selected from the group consisting of:

[0102]

[0103]

[0104] Where X 1 -X 61 Each independently is C or N;

[0105] Where X 17 -X 22 At least two of them are N;

[0106] where Y 1 , Y 2 and Y 3 Each independently selected from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO 2 , SiRR', GeRR' and P(O)R;

[0107] wherein Z is selected from the group consisting of B, Al, Ga, PO and N;

[0108] Where R A , RB , R C , R D , R E , R F , R G , R H , R I , R J , R K , R L , R M , R N and R O Each independently represents a single substitution to the maximum number of substitutions allowed;

[0109] Each 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 , R N and R O are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof;

[0110] Each L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are independently a direct bond or an organic linking group; and

[0111] Any two substituents may be joined or fused to form a ring.

[0112] In some embodiments, each 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 , R N and R O are independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0113] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula I.

[0114] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula I, and X 1 -X 8 At least one of them is N.

[0115] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula I, and X 1 -X 8 Exactly one of them is N.

[0116] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula I, and X 1 -X 8 All are C.

[0117] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 It is NR.

[0118] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 For NH.

[0119] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 is O.

[0120] In some embodiments, R 1 , R2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 For S.

[0121] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 For Se.

[0122] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula I, and L 1 For direct keys.

[0123] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula I, and L 1 Contains phenyl.

[0124] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula II.

[0125] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula II, and X 9 -X 16 At least one of them is N.

[0126] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula II, and X 9 -X 16 Exactly one of them is N.

[0127] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula II, and X 9 -X 16 All are C.

[0128] In some embodiments, R 1 , R 2 and R 3 At least one of them comprises a structure of Formula II, and L 2 For direct keys.

[0129] In some embodiments, R 1 , R 2 and R 3 At least one of them comprises a structure of Formula II, and L 2 Contains phenyl.

[0130] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula III.

[0131] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 At least one of them is N.

[0132] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 Exactly one of them is N.

[0133] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 At least two of them are N.

[0134] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 Exactly two of them are N.

[0135] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 Exactly three of them are N.

[0136] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 All are C.

[0137] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula III, and L 3 For direct keys.

[0138] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula III, and L 3 Contains phenyl.

[0139] In some embodiments, R 1 , R 2 and R 3 At least one of them comprises a structure of Formula III, and both R E Connect to X that is not N 17 -X 22 A carbazole group in .

[0140] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula IV.

[0141] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and X 23 -X 33 At least one of them is N.

[0142] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and X 23 -X 33 Exactly one of them is N.

[0143] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and X 23 -X 33 Exactly two of them are N.

[0144] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and X 23 -X 33All are C.

[0145] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Z is B.

[0146] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Y 2 is O.

[0147] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Y 3 is O.

[0148] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Y 2 and Y 3 Both are O.

[0149] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and L 4 For direct keys.

[0150] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and L 4 Contains phenyl.

[0151] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula V.

[0152] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X 34 -X 45 At least one of them is N.

[0153] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X34 -X 45 Exactly one of them is N.

[0154] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X 34 -X 45 At least two of them are N.

[0155] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X 34 -X 45 Exactly two of them are N.

[0156] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X 34 -X 45 At least three of them are N.

[0157] In some embodiments, R 1 , R 2 and R 3 At least one of them comprises a structure of Formula V, and L 5 For direct keys.

[0158] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula V, and L 5 Contains phenyl.

[0159] In some embodiments, R 1 , R 2 and R 3 At least one of the compounds comprises a structure of Formula VI.

[0160] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45 At least one of them is N.

[0161] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45Exactly one of them is N.

[0162] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45 At least two of them are N.

[0163] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45 Exactly two of them are N.

[0164] In some embodiments, R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45 At least three of them are N.

[0165] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula VI, and L 6 For direct keys.

[0166] In some embodiments, R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula VI, and L 6 Contains phenyl.

[0167] In some embodiments, R 1 , R 2 and R 3 At least one of the monovalent or multivalent forms comprises a structure selected from the group consisting of:

[0168]

[0169]

[0170]

[0171]

[0172] Each R DD -R GG independently represents mono-substitution to the maximum possible number of substitutions or no substitution;

[0173] Each R DD -R GG and R N are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof;

[0174] Where X 4 To X 27 Each independently is C or N;

[0175] wherein A is selected from the group consisting of: B, N, P, PO, CR, SiR, GeR,

[0176] Where L 1 -L 2 Each independently selected from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO 2 , SiRR', GeRR' and P(O)R.

[0177] In some embodiments, the compound is selected from the group consisting of:

[0178]

[0179]

[0180]

[0181] In some embodiments, the compound is selected from the group consisting of:

[0182]

[0183]

[0184]

[0185]

[0186]

[0187] wherein i is an integer from 469 to 575, and j, k, l and m are each independently an integer from 1 to 575, wherein R1 to R575 have the following structure:

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215] In some embodiments, the compound is selected from the group consisting of:

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235] In some embodiments, the formula R described herein 1 R 2 R 3ML-M' compounds may 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., hydrogen or deuterium positions) occupied by deuterium atoms. In some embodiments, one or more hole transport moieties are partially or fully deuterated. In some embodiments, one or more electron transport 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.

[0236] In yet another aspect of the present disclosure, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: a solvent, an emitter, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

[0237] The present disclosure encompasses any chemical structure comprising a novel compound of the present disclosure or a monovalent or multivalent variant thereof. In other words, the compounds of the present invention or their monovalent or multivalent variants may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also referred to as supermolecules). As used herein, "monovalent variants of a compound" refers to the same part as the compound, but one of the hydrogens has been removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variants of a compound" refers to the same part as the compound, but more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds. As used in this context, the description that structure A includes part B means that structure A includes the structure of part B, and the structure of part B does not include H or D atoms that can be connected to part B. This is because at least one H or D on a given part structure must be replaced with a substituent so that part B can be a part of structure A, and after it becomes a part of structure A, one or more of the H or D on a given part B structure may be further substituted.

[0238] C. OLEDs and Devices of the Present Disclosure

[0239] In another aspect, the present disclosure also provides an OLED device comprising a first organic layer, the first organic layer containing a compound as disclosed in the above compound section of the present disclosure.

[0240] In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a compound described herein.

[0241] In some embodiments, the organic layer may be an emission layer.In some embodiments, the organic layer is selected from the group consisting of: a HIL, a HTL, an EBL, an EML, a HBL, an ETL, and an EIL.

[0242] In some embodiments, the compound can be a host, and the first organic layer can be an emission layer comprising 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 T1 to S0 state. Most of the Ir and Pt complexes currently used in OLEDs are phosphorescent emitters. In some embodiments, if the excited complex formation involves a triplet emitter, such excited complexes can also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to photon emission when the electron spin quantum number does not change, such as from S1 to S0 state or from D1 to D0 state. The fluorescent emitter can be a delayed fluorescent or non-delayed fluorescent emitter. Depending on the spin state, the fluorescent emitter can be a singlet emitter or a doublet emitter or other multiplet emitter. 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 produced by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but on the thermal population between the triplet and singlet excited states. Thermal energy can activate the triplet transition back to the singlet state. This type of delayed fluorescence is also called TADF. E-type delayed fluorescence characteristics 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 complexes. There are two main types of TADF emitters, one is called donor-acceptor type TADF and the other is called multi-resonance (MR) TADF. Typically, a single compound donor-acceptor TADF compound is constructed by connecting an electron donor portion (such as an amino or carbazole derivative) and an electron acceptor portion (such as an N-containing six-membered aromatic ring or a cyano-substituted aromatic ring). A donor-acceptor excited complex can be formed between a hole transport compound and an electron transport compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials contain boron, carbon, and nitrogen atoms. Such materials may also contain other atoms, such as oxygen. In some embodiments, the reverse intersystem crossing time from T1 to S1 of delayed fluorescence emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time may be greater than 10 microseconds and less than 100 microseconds.

[0243] In some embodiments, the compound is a host and the organic layer is an emissive layer comprising a phosphorescent or fluorescent material.

[0244] In some embodiments, the emissive dopant may be a phosphorescent or fluorescent material.

[0245] In some embodiments, the non-emissive dopant may also be a phosphorescent or fluorescent material.

[0246] In some embodiments, the OLED may include additional compounds selected from the group consisting of: non-delayed fluorescent materials, delayed fluorescent materials, phosphorescent materials, and combinations thereof.

[0247] 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 phosphorescent material energy 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 comprises an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material (e.g., a host material, an emitter material) within the OLED.

[0248] In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an emitter that emits light in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material does not emit light in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material energy transfers its excited state to another material in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material participates in charge transport in the OLED. In some embodiments, the non-delayed fluorescent material or delayed fluorescent material is an acceptor, and the OLED further comprises a sensitizer.

[0249] In some embodiments, the compound may be an acceptor, and the OLED may further include a sensitizer selected from the group consisting of a delayed fluorescent material, a phosphorescent material, and combinations thereof.

[0250] In some embodiments, the compound can be a non-delayed fluorescent emitter, a delayed fluorescent emitter, or a component of an exciplex that is a non-delayed fluorescent emitter or a delayed fluorescent emitter. 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. Narrower FWHM means better color purity for OLED display applications.

[0251] In some embodiments, the compound is a host and the OLED comprises an acceptor as an emitter and a sensitizer selected from the group consisting of a delayed fluorescent material, a phosphorescent material, and combinations thereof; wherein the sensitizer transfers energy to the acceptor.

[0252] In some embodiments, the phosphorescent material may 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 ;

[0253] Where L 1 , L 2 and L 3 Can be the same or different;

[0254] where x is 1, 2, or 3;

[0255] Where y is 0, 1 or 2;

[0256] where z is 0, 1 or 2;

[0257] Wherein x+y+z is the oxidation state of the metal M;

[0258] Where L 1 Selected from the group consisting of structures in the following ligand list:

[0259]

[0260]

[0261]

[0262]

[0263] Among them, each L 2 and L 3 Independently selected from the group consisting of: and a structure in the ligand list; wherein:

[0264] M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag and Cu;

[0265] T is selected from the group consisting of B, Al, Ga and In;

[0266] K 1 ' is a direct key or is selected from the group consisting of: NR e , PR e , O, S and Se;

[0267] Each Y 1 To Y 15 independently selected from the group consisting of: carbon and nitrogen;

[0268] Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO 2 , CR e R f 、SiR e R f and GeR e R f ;

[0269] R e and R f capable of being fused or joined to form a ring;

[0270] Each R a , Rb , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

[0271] 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 general substituents defined herein; and

[0272] Any two of the substituents can be fused or joined to form a ring or to form a multidentate ligand.

[0273] In some embodiments, the phosphorescent material has a structural 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 );

[0274] Where L A , L B and L C They are different from each other in Ir compounds;

[0275] Where L A and L B may be the same or different in the Pt compound; and

[0276] Where L A and L B Capable of linking to form a tetradentate ligand in the Pt compound.

[0277] In some embodiments, the phosphorescent material is selected from the group consisting of the following dopant group 1:

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284] in

[0285] X 96 To X 99 Each of is independently C or N;

[0286] Each Y 100 Independently selected from the group consisting of: NR", O, S and Se;

[0287] R 10a , R 20a , R 30a , R 40a and R 50a Each of the above independently represents mono- to maximal substitution, or no substitution;

[0288] 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 of is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0289] In some embodiments, the phosphorescent material is selected from the group consisting of the following dopant group 2:

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298] in:

[0299] Each Y 100 Independently selected from the group consisting of: NR", O, S and Se;

[0300] L is independently selected from the group consisting of: direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR", C=CR"R"', S=O, SO 2 , CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof;

[0301] X 100 and X 200 at each occurrence selected from the group consisting of: O, S, Se, NR" and CR"R"';

[0302] Each R A" , R B" , R C" , R D" , R E" and R F" independently represents mono- to maximum-substitution, or no substitution;

[0303] 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 is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0304] In some embodiments of the above dopant groups 1 and 2, each unsubstituted aromatic carbon atom may be replaced by N to form a nitrogen heterocycle. In some embodiments, the maximum number of N atoms in one ring is 1 or 2. In some embodiments of the above dopant group 2, each Pt atom in the formula may be replaced by a Pd atom.

[0305] In some embodiments of the OLED, the delayed fluorescent material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescent material is a metal complex. In some embodiments, the delayed fluorescent material is a non-metallic complex. In some embodiments, the delayed fluorescent material is a Zn, Cu, Ag or Au complex.

[0306] In some embodiments of OLEDs, the delayed fluorescent material has the formula M(L 5 )(L 6 ), where M is Cu, Ag or Au, L 5 and L 6 Different, and L 5 and L 6 Independently selected from the group consisting of:

[0307]

[0308]

[0309] Among them A 1 -A 9 are each independently selected from C or N;

[0310] Each R P , R Q and R U independently represents mono- to maximum-substitution, or no substitution;

[0311] Among them, each R P , R P , R U , R SA , R SB , R RA , R RB , R RC , R RD , R RE and R RF is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents can be joined or fused to form a ring.

[0312] In some embodiments of the OLED, the delayed fluorescent material is selected from the group consisting of structures in the following TADF list:

[0313]

[0314]

[0315] In some embodiments of the OLED, the delayed fluorescent material comprises at least one of the donor moieties selected from the group consisting of:

[0316]

[0317]

[0318] where Y T , Y U , Y V and Y W Each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O and SO 2 .

[0319] In some of the above embodiments, any carbon ring atom, up to a total of three carbon ring atoms together with their substituents, in each benzene ring of any of the above structures can be replaced by N.

[0320] In some embodiments, the delayed fluorescent material comprises at least one of an 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 linked, via a conjugated linker or a non-conjugated linker (such as sp 3 carbon or silicon atoms).

[0321] In some embodiments, the fluorescent material comprises at least one of the chemical moieties selected from the group consisting of:

[0322]

[0323]

[0324]

[0325] where Y F , Y G , Y H and Y I Each independently selected from the group consisting of: B, C, Si, Ge, N, P, O, S, Se, C=O, S=O and SO 2 ;

[0326] Where X F and X G are each independently selected from the group consisting of C and N.

[0327] In some of the above embodiments, any carbon ring atom, up to a total of three carbon ring atoms together with their substituents, in each benzene ring of any of the above structures can be replaced by N.

[0328] In yet another aspect, the OLED of the present disclosure may also include an emission region containing a compound or formulation of compounds as disclosed in the above compound section of the present disclosure. In some embodiments, the emission region may include a compound or formulation of compounds described herein. In some embodiments, the emission region is composed 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 found in U.S. Patent Application Publication No. 2023 / 0292605, and the entire contents are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or formulation of a compound as disclosed in Sections A and D of the present disclosure.

[0329] In some embodiments, the OLED or emission region 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 includes at least one pixel, wherein the at least one pixel includes a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED, which includes a first emission region. The second sub-pixel includes a second OLED, which includes a second emission region. In some embodiments, the first and / or second OLED, the first and / or second emission regions may be the same or different and each may 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.

[0330] In some embodiments, the first emission region is configured to emit a wavelength having a peak wavelength λ max1 The second emission region is configured to emit light having a peak wavelength λ max2In some embodiments, the peak wavelength λ max1 With λ max2 The difference between is at least 4 nm but within the same color. For example, light blue and dark blue light as described above. In some embodiments, the first emission region is configured to emit a light having a peak wavelength λ in one region of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm. max1 and the second emission region is configured to emit light having a peak wavelength λ in one of the remaining regions of the visible spectrum of 400-500nm, 500-600nm, 600-700nm max2 light. In some embodiments, the first emission region comprises (if more than one) a first number of emission layers deposited one on top of the other; and the second emission region comprises (if more than one) a second number of emission layers deposited one on top of the other; 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, which may be the same or different. In some embodiments, the first emission region comprises a phosphorescent material and the second emission region comprises a fluorescent material. In some embodiments, both the first emission region and the second emission region comprise fluorescent materials, which may be the same or different.

[0331] In some embodiments, at least one pixel of an OLED or an emissive region comprises a total of N subpixels; wherein the N subpixels comprise a first subpixel and a second subpixel; wherein each of the N subpixels comprises an emissive region; wherein the total number of emissive regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emissive region is identical to the first emissive region; and each subpixel of at least one pixel comprises an emissive region that is identical to the first emissive region. In some embodiments, a full-color pixel arrangement may have a plurality of pixels comprising a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region is different from a corresponding display feature in the second pixel region, and wherein at least one display feature is selected from the group consisting of: resolution, cavity mode, color, outcoupling, and color filter.

[0332] 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 features as described above for pixelated devices. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more of the emission regions in the pixelated OLED or stacked OLED comprises a sensitizer and an acceptor having various sensitizing device features and various embodiments of the compounds of the present invention disclosed herein. For example, the first emission region is included in the sensitizing device, while the second emission region is not included in the sensitizing device; in some cases, both the first emission region and the second emission region are included in the sensitizing device.

[0333] In some embodiments, the OLED can emit light having at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99% or 100% from a plasmon mode. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emission layer is used as an enhancement layer. The enhancement layer comprises a plasmon material exhibiting a surface plasmon resonance, the plasmon material non-radiatively couples to the emitter material, and transfers excited state energy from the emitter material to a non-radiative mode of a surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance from the organic emission layer that does not exceed a threshold distance, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. 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 emitting material in the absence of the enhancement layer.

[0334] In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the side of the enhancement layer opposite to the organic emission layer. The outcoupling layer scatters energy from surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from the surface plasmon mode of the device into other modes, such as but not limited to an organic waveguide mode, a substrate mode, or another waveguide mode. In some embodiments, one or more intermediate layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intermediate layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and / or mixtures of these materials.

[0335] The enhancement layer changes the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, changed emission line shape, variation in emission intensity with angle, changed emitter material stability, changed OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both, 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 OLED according to the present disclosure may also include any other functional layers commonly found in OLEDs.

[0336] In some embodiments, the enhancement layer may include 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: 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 configured as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or has sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged.

[0337] In some embodiments, the outcoupling layer has wavelength-sized features or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles. In some embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outcoupling layer may be adjusted by at least one of: 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 may be formed of at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials, and / or a core of one type of material and coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the outcoupling layer is formed by photolithography.

[0338] In some embodiments of plasmonic devices, the emitter and / or host compound used in the emissive 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.

[0339] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound or a formulation of compounds as disclosed in the above compound section of the present disclosure.

[0340] In some embodiments, a consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as described herein.

[0341] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an electric 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 oppositely charged electrode. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a light emission mechanism, light is emitted. In some cases, the exciton can be localized into an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0342] Figure 1 An organic light-emitting device 100 is shown. The figures are not necessarily drawn to scale. The device 100 may 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. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be manufactured by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in US 7,279,704, columns 6-10, which are incorporated by reference.

[0343] More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is one doped with F at a molar ratio of 50:1. 4 -TCNQ m-MTDATA, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal (e.g., Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0344] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be manufactured by depositing the layers in order. Because the most common OLED configuration has a cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100 .

[0345] Figure 1 and 2The simple layered structures described in are provided by way of non-limiting examples, and it should be understood that embodiments of the present disclosure may be used in conjunction with various 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 omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than the specifically described materials may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that a combination of materials may be used, such as a mixture of a host and a dopant, or more generally, a mixture. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, Figure 1 and 2 Multiple layers of said different organic materials.

[0346] Structures and materials not specifically described may also be used, such as OLEDs containing polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0347] Unless otherwise specified, any 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, 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., incorporated by reference in their entirety), and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)) (as described in U.S. Pat. No. 7,431,968, incorporated by reference in their 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 material to be deposited may be modified to make it compatible with a specific deposition method. For example, branched or unbranched, preferably containing at least 3 carbons, such as alkyl and aryl substituents, may be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 or more carbons may be used, and 3 to 20 carbons are a preferred range. Materials having asymmetric structures may have better solution processability than materials having symmetric structures because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to withstand solution processing.

[0348] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from exposure to harmful substances in an environment including moisture, vapor and / or gas, etc. The barrier layer can be deposited on the substrate, the electrode, under the substrate, the electrode, or beside the substrate, the electrode, or on any other part of the device (including the edge). The barrier layer may include a single layer or multiple layers. The barrier layer can be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having multiple phases. Any suitable material or material combination can be used for the barrier layer. The barrier layer may be combined with an inorganic compound or an organic compound or both. The preferred barrier layer includes a plurality of alternative layers of polymeric materials and non-polymeric materials; organic materials and inorganic materials; or a mixture of polymeric materials and non-polymeric materials, as described in an example in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety.

[0349] The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of the electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronic devices and / or power supplies. The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of consumer products, and the consumer products have one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, and the OLED includes a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product containing one or more of one or more light sources and / or a certain type of visual display. Some examples of consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. Various control mechanisms can be used to control devices manufactured according to the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0350] More details regarding OLEDs and the definitions set forth above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0351] 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.

[0352] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. These quantum dots can be in the emission layer, or in other functional layers, such as downconversion layers.

[0353] In some embodiments, the OLED comprises 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 having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having 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.

[0354] D. Other materials used in OLED

[0355] The materials described herein are various examples of specific layers that can be used in OLEDs. They 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 by the host materials in the EML themselves, or in combination with a wide variety of other emitters, hosts, transport layers, barrier 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.

[0356] a) Conductive dopants:

[0357] The charge transport layer can be doped with a conductivity dopant to substantially change its charge carrier density, which in turn will change its conductivity. The 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 conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer. In some embodiments, the conductive dopant comprises at least one chemical moiety selected from the group consisting of: a cyano group, a fluorinated aryl or heteroaryl group, a fluorinated alkyl or cycloalkyl group, an alkylene group, a heteroaryl group, an amide, a benzodithiophene, and a highly conjugated heteroaryl group extended by a non-cyclic double bond.

[0358] b)HIL / HTL:

[0359] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoO x ; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0360] Examples of aromatic amine derivatives for use in HIL or HTL include, but are not limited to, the following general structure:

[0361]

[0362] Ar 1 To Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon cyclic compounds: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, 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, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Ar 1 To Ar 9 Each of may be unsubstituted or may be substituted with a general substituent as described above, and any two substituents may be joined or fused to form a ring.

[0363] In some embodiments, each Ar 1 To Ar 9 independently comprising a portion selected from the group consisting of:

[0364]

[0365] 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.

[0366] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0367]

[0368] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 The coordinating atoms of L are independently selected from C, N, O, P and S; 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.

[0369] In some embodiments, (Y 101 -Y 102 ) is a 2-phenylpyridine or 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 relative + / Fc coupling is less than the minimum oxidation potential in solution of about 0.6 V.

[0370] In some embodiments, the HIL / HTL material is selected from the group consisting of phthalocyanine and porphyrin compounds, starburst triarylamines, CF x Fluorocarbon polymers, conductive polymers (e.g., PEDOT:PSS, polyaniline, polythiophene), phosphonic acid and silane SAMs, triarylamine or polythiophene polymers containing conductive dopants, organic compounds containing conductive inorganic compounds (such as molybdenum oxide and tungsten oxide), n-type semiconductive organic complexes, metal organic metal complexes, crosslinkable compounds, polymers and copolymers based on polythiophene, triarylamines, triarylamines containing spirofluorene cores, arylamine carbazole compounds, triarylamines containing (di)benzothiophene / (di)benzofuran, indolecarbazoles, isoindole compounds and metal carbene complexes.

[0371] c) EBL:

[0372] 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 produce substantially higher efficiency and / or longer lifetimes than similar devices lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than 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 energy level of the compound used in the EBL is shallower than the HOMO energy level 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 used in one of the hosts described below.

[0373] d) Other entities:

[0374] 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 host materials 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 include two hosts: a first host and a second host. In some embodiments, the first host is a hole transport host, and the second host is an electron transport host. In some embodiments, the first host is a hole transport host, and the second host is a bipolar host. In some embodiments, the first host is an electron transport 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 include a third host. In some embodiments, the third host is selected from the group consisting of: an insulating host (wide bandgap host), a hole transport host, and an electron transport 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 include a fourth host. In some embodiments, the fourth host is selected from the group consisting of: an insulating host (wide bandgap host), a hole transport host, and an electron transport host. In some embodiments, the fourth host forms an excited complex 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 transport host is less than -2.4eV, less than -2.5eV, less than -2.6eV or less than -2.7eV. In some embodiments, the HOMO of the hole transport host is higher than -5.6eV, higher than -5.5eV, higher than -5.4eV or higher than -5.35eV. HOMO and LUMO values ​​can be determined using solution electrochemistry. A CH Instruments model 6201B potentiostat can be used to perform solution cyclic voltammetry and differential pulse voltammetry with anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as supporting electrolytes. Glassy carbon, platinum wire and silver wire are used as working electrode, counter electrode and reference electrode, respectively. The electrochemical potential can be referenced to the internal ferrocene-ferrocenium redox couple (Fc / Fc+) by measuring the peak potential difference by differential pulse voltammetry.The corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were determined by reference to the cationic and anionic redox potentials of ferrocene (4.8 eV vs. vacuum) according to literature references ((a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W., Chem. Mater. 1998, 10, 3620-3625.; (b) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, RF; Bassler, H.; Porsch, M.; Daub, J. Adv. Mater. 1995, 7, 551).

[0375] In some embodiments, the compounds of the invention described herein may be used as one of the subjects described above, and the compounds described below may be used as one or more of the other subjects described above.

[0376] Examples of metal complexes used as one or more other hosts preferably have the following general formula:

[0377]

[0378] Where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 The coordinating atoms of L are independently selected from C, N, O, P and S; 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.

[0379] In some embodiments, the metal complex is:

[0380]

[0381] wherein (ON) is a bidentate ligand having a metal coordinated to O and N atoms.

[0382] In some embodiments, Met is selected from Ir and Pt. In other embodiments, (Y 103 -Y 104 ) is a carbene ligand.

[0383] In some embodiments, the one or more other entities contain at least one selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, 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-indolecarbazole, aza-triphenylene, aza-tetraphenylene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene; and a group consisting of 2 to 10 cyclic structural units, the cyclic structural units are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option in each group may be unsubstituted or may be substituted with a general substituent as described herein or may be further condensed.

[0384] In some embodiments, the one or more other bodies include at least one of the parts selected from the group consisting of:

[0385]

[0386]

[0387] Where k is an integer from 0 to 20 or from 1 to 20. 101 To X 108 Z is independently selected from C or N. 101 and Z 102 are independently selected from C, N, O or S.

[0388] In some embodiments, the one or more other hosts are selected from the group consisting of: aryl carbazoles, metal 8-hydroxyquinolinates (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, Compounds, aryltriphenylene compounds, poly-fused heteroaryl compounds, donor-acceptor molecules, dibenzofuran / dibenzothiophene compounds, polymers (e.g., PVK), spirofluorene compounds, spirofluorene-carbazole compounds, indolecarbazole, 5-membered electron-deficient heterocycles (e.g., triazole, oxadiazole), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al containing N^N ligands), dibenzothiophene / dibenzofuran-carbazole compounds, silicon / germanium aromatic compounds, aromatic benzoyl esters, carbazoles connected by non-conjugated groups, aza-carbazole / dibenzofuran / dibenzothiophene compounds and high triplet metal organic metal complexes (e.g., metal-carbene complexes).

[0389] In some embodiments, the one or more other hosts comprise at least one chemical group selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boronaphtho[3,2,1-de]anthracene, azacyclohexaborane, oxaborabine, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, 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-boronaphtho[3,2,1-de]anthracene).

[0390] In some embodiments, the one or more other bodies can be selected from the group consisting of structures in the following body group 1:

[0391]

[0392]

[0393]

[0394]

[0395]

[0396]

[0397]

[0398] in:

[0399] J 1 To J 6 Each of is independently C or N;

[0400] L' is a direct bond or an organic linker;

[0401] Each Y AA , Y BB , Y CC and Y DD independently selected from the group consisting of: absent, bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0402] R A '、R B '、R C '、R D '、R E '、R F ' and R G Each of ' independently represents mono-substituted to maximum substitution, or no substitution;

[0403] 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 consisting of general substituents as defined herein; any two substituents can be joined or fused to form a ring;

[0404] Also, where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

[0405] In some embodiments, J 1 To J 3 At least one of is N, and in some embodiments, J 1 To J 3 At least two of them are N. In some embodiments, J 1 To J 3 All three of Y are N. In some embodiments, each Y CC and Y DD Preferred are O, S and SiRR', and more preferred are O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen heterocycle.

[0406] In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 of formula EGa-MGb-EGc, or when MGb is absent, EG1-EG1 to EG53-EG53 of formula EGa-EGc, wherein 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:

[0407]

[0408]

[0409] The structures of MG1 to MG27 are shown below:

[0410]

[0411]

[0412] In the MGb structures presented above, the two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0413] In some embodiments, the host can be any of its aza-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 by the following Host Group 2 List, wherein each of MGb, EGa, and EGc is defined as follows:

[0414]

[0415]

[0416] In the above table, EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are annotated with a numerical prefix indicating their bonding position in the MGb structure.

[0417] e) Emitter materials in EML:

[0418] One or more emitter materials may be used in combination with the compounds or devices disclosed herein. The emitter material may be emissive or non-emissive in the current device as described herein. Examples of emitter materials are not particularly limited, and any compound may be used as long as the compound is capable of producing 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 a combination of these methods.

[0419] f)HBL:

[0420] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime than a similar device lacking the blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or higher triplet energy than one or more emitters closest to the HBL interface.

[0421] In some embodiments, the compounds used in HBL contain the same molecules or the same functional groups as used in the subjects described above.

[0422] In some embodiments, the compound used in HBL comprises at least one of the following moieties selected from the group consisting of:

[0423]

[0424] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0425] g)ETL:

[0426] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0427] In some embodiments, the compounds used in the ETL comprise at least one of the following moieties in the molecule:

[0428] and fullerene; wherein k is an integer from 1 to 20, X 101 To X108 Selected from C or N; Z 101 Selected from the group consisting of C, N, O and S.

[0429] In some embodiments, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0430]

[0431] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; 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.

[0432] 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 electron-deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzimidazole), thiole compounds, arylborane compounds, fluorinated aromatic compounds, fullerenes (e.g., C60), triazine complexes, and Zn(N^N) complexes.

[0433] h) Charge Generation Layer (CGL)

[0434] In a tandem or stacked OLED, the CGL plays a fundamental role in the 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 electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n- and p-conductivity dopants used in the transport layer.

[0435] In any compound disclosed herein, hydrogen atoms can be partially or completely 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 deuteration percentage has its common meaning and includes the percentage of all possible hydrogens and deuterium atoms replaced by deuterium atoms. In certain embodiments, the deuterium atom is connected to an aromatic ring. In certain embodiments, the deuterium atom is connected to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atom is connected to a heteroatom, such as a Si or Ge atom.

[0436] It should be understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the present invention. For example, other materials and structures may be used to replace many materials and structures described herein without departing from the spirit of the present invention. The present invention as required may therefore include variations of 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 about why the present invention works are not intended to be restrictive.

[0437] Experimental data

[0438] Synthesis of Compound 1 of the Invention

[0439] Synthesis of (3-chlorophenyl)diphenylsilane: A 100 mL two-necked flask was evacuated and backfilled with nitrogen. Tetrahydrofuran (20.00 mL) and chlorodiphenylsilane (1.500 g, 1.342 mL, 1 eq., 6.857 mmol) were added and cooled to 0 ° C. (3-chlorophenyl)magnesium bromide (2.219 g, 20.57 mL, 0.500 mole, 1.5 eq., 10.29 mmol) in THF was slowly added and the reaction mixture was stirred at room temperature for 5 hours. The crude product was chromatographed on silica (120 g×2, heptane). A clear liquid (1.74 g, 86% yield) was obtained.

[0440] Synthesis of 1,3-bis(3-chlorophenyl)-1,1,3,3-tetraphenyldisiloxane: (3-Chlorophenyl)diphenylsilane (250.0 mg, 1 eq., 847.9 μmol) was evacuated and backfilled with nitrogen. Dichloromethane (4.000 mL) and 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]aziridine (258.2 mg, 253.6 μL, 2 eq., 1.696 mmol) were added, and the reaction mixture was heated at 40° C. for 16 hours. The crude product was chromatographed on silica (80 g×2, DCM / Hep=1 / 4) to give 1,3-bis(3-chlorophenyl)-1,1,3,3-tetraphenyldisiloxane (150 mg, 58.6% yield).

[0441] Synthesis of Compound 1 of the present invention: A mixture of 1,3-bis(3-chlorophenyl)-1,1,3,3-tetraphenyldisiloxane (690.0 mg, 1 equivalent, 1.143 mmol), 9H-carbazole (420.5 mg, 2.2 equivalents, 2.515 mmol), Pd(allyl)Cl dimer (12.55 mg, 0.03 equivalents, 34.29 μmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (48.35 mg, 0.12 equivalents, 137.2 μmol) and sodium 2-methylpropan-2-ol (274.6 mg, 2.5 equivalents, 2.857 mmol) was evacuated and backfilled with nitrogen. Toluene (5.000 mL) was added and the reaction mixture was refluxed for 30 minutes. The crude product was chromatographed on silica (120 g×3, DCM / Hep=1 / 2) to obtain the present compound 1 (587 mg, 59% yield)

[0442] Synthesis of Compound 2 of the Invention

[0443] Synthesis of Compound 2 of the present invention: A mixture of 1,3-bis(3-chlorophenyl)-1,1,3,3-tetraphenyldisiloxane (690.0 mg, 1 equivalent, 1.143 mmol), 9H-3,9'-dicarbazole (840 mg, 2.2 equivalents, 2.515 mmol), Pd(allyl)Cl dimer (12.55 mg, 0.03 equivalents, 34.29 μmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (48.35 mg, 0.12 equivalents, 137.2 μmol) and sodium 2-methylpropan-2-ol (274.6 mg, 2.5 equivalents, 2.857 mmol) was evacuated and backfilled with nitrogen. Toluene (5.000 mL) was added and the reaction mixture was refluxed for 30 minutes. The crude product was chromatographed on silica (120 g×3, DCM / Hep=1 / 2) to obtain the present compound 1 (273 mg, 20% yield)

[0444] Table 1. Photophysical properties

[0445]

[0446]

[0447] Table 1 summarizes the T1, HOMO, LUMO values ​​of the inventive compounds 1-2. For the inventive compound 1, all properties were determined through the 9-phenyl-9H-carbazole moiety, and for the inventive compound 2, the properties were tracked through the 9-phenyl-9H-3,9'-dicarbazole moiety. This is desirable because the Si-O-Si moiety of the present invention does not affect the physical properties that are already built into the current PhOLED device architecture. In fact, the inventive features impart additional steric effects and rotatable Si-O bonds so that the host molecules do not pack too tightly due to steric effects to maintain high solid-state T1, but have more opportunities to form good transport channels due to additional flexibility.

[0448] Table 2. Device performance

[0449]

[0450] OLEDs were grown on glass substrates pre-coated with a 15-Ω / sq layer of indium tin oxide (ITO). Prior to any organic layer deposition or coating, the substrates were degreased with solvent and then treated with oxygen plasma at 100 mTorr, 50 W for 1.5 min and UV ozone for 5 min.

[0451] The devices in Table 2 were fabricated by thermal evaporation in high vacuum (<10-6 Torr). The anode electrode was Starting from the ITO surface, the organic layers of the device example are composed of the following in sequence: Compound 1 (HIL), Compound 2 (HTL), Compound 3 (EBL), Compound 3 (EML) doped with 50% of compound 5 and 15% of a host (compound 1 of the present invention or a comparative example) and 12% of an emitter, Compound 4 (BL), Compound 5 doped with 35% of compound 6 (ETL), Compound 5 (EIL), followed by After fabrication, the cathode was placed in a nitrogen glove box (<1 ppm H 2 O and O 2 ) All devices were immediately encapsulated with a glass lid sealed with epoxy resin, and a moisture absorber was incorporated into the interior of the package. The doping percentage is in volume percentage.

[0452]

[0453] The OLED devices detailed in Table 2 provide an overview of the device performance of the compound emitter 1 of the present invention and the comparative example. Unexpectedly, the compounds of the present invention exhibit better performance in terms of EQE, voltage and lifetime, and present a more saturated CIEy. The improvements shown here exceed any value attributable to experimental error, and the observed improvements are significant. This result shows that even without any structural and device optimization, the subject of the present invention can achieve very promising results, even better than the well-known and widely incorporated stable subject (comparative example). This opens up a way for the range of chemicals in the subject design for achieving the desired quality of commercial OLED products.

[0454] Solution cyclic voltammetry and differential pulse voltammetry were performed using a CH instrument model 6201B potentiostat, using anhydrous dimethylformamide solvent and tetrabutylammonium hexafluorophosphate as supporting electrolyte. Glassy carbon and platinum and silver wires were used as working electrodes, counter electrodes, and reference electrodes, respectively. The electrochemical potential was referenced to the internal ferrocene-ferrocene salt redox pair (Fc / Fc+) by measuring the peak potential difference by differential pulse voltammetry. The corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were determined by reference to the cationic and anionic redox potentials (4.8 eV vs. vacuum) for ferrocene according to the literature ((a) Fink; Heischkel; Serracart; Schmidt, Chemical Materials, 1998, 10, 3620-3625.; (b) Pomerin; Westweber; Geis; Macht; Basler; Porsche; Dobb, Journal of Advanced Materials, 1995, 7, 551).

[0455] The T1 energies were obtained from the emission spectrum of frozen samples in 2-MeTHF at 77 K.

Claims

1. A type R 1 R 2 R 3 ML-M' compounds, in M is Si or Ge; L is selected from the group consisting of direct bonds or from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO2, SiRR', GeRR' and P(O)R; When L is a direct bond, M' is SiR 4 R 5 R 6 or GeR 4 R 5 R 6 ; When L is not a direct bond, M' is SiR 4 R 5 R 6 ,GeR 4 R 5 R 6 or one or more hydrocarbon groups, provided that at least one of the one or more hydrocarbon groups is a carbocyclic group; Each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; Any two substituents can be joined or fused to form a ring; R 1 , R 2 and R 3 at least one of which comprises a structure selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, silane, fluorine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, and aza variants thereof; The conditions are: If L is a direct bond and both M and M' contain Si, then R 1 , R 2 and R 3 At least one of the following comprises benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim) or borane, or R 1 , R 2 and R 3 together form two structures selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole and aza variants thereof, with the additional proviso that the same R 1 , R 2 and R 3 Does not constitute dicarbazole; If M is Si, then R 1 , R 2 and R 3 At least two of them are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; If M' is SiR 4 R 5 R 6 , then R 4 , R 5 and R 6 At least two of are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; and The compounds contain no non-ring N atoms.

2. The compound according to claim 1, wherein each of R, R', R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof; and / or wherein L is O.

3. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the structures comprises a structure selected from the group consisting of: Where X 1 -X 61 Each independently is C or N; Where X 17 -X 22 At least two of them are N; where Y 1 , Y 2 and Y 3 Each independently selected from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO2, SiRR', GeRR' and P(O)R; wherein Z is selected from the group consisting of B, Al, Ga, PO and N; Where 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 , R N and R O Each independently represents a single substitution to the maximum number of substitutions allowed; Each 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 , R N and R O are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; Each L 1 , L 2 , L 3 , L 4 , L 5 and L 6 are independently a direct bond or an organic linking group; and Any two substituents may be joined or fused to form a ring.

4. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 NR; or R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula I, and Y 1 is O.

5. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula II, and X 9 -X 16 All C; and / or R 1 , R 2 and R 3 At least one of them comprises a structure of Formula II, and L 2 is a direct key; and / or R 1 , R 2 and R 3 At least one of them comprises a structure of Formula II, and L 2 Contains phenyl.

6. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 At least one of is N; and / or R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula III, and X 17 -X 22 All are C.

7. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula IV, and X 23 -X 33 All C; and / or R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Z is B; and / or R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula IV, and Y 2 and Y 3 Both are O.

8. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula V, and X 34 -X 45 At least one of is N; and / or R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula V, and L 5 is a direct key; and / or R 1 , R 2 and R 3 At least one of them comprises a structure of Formula V, and L 5 Contains phenyl.

9. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the following comprises a structure of Formula VI, and X 34 -X 45 At least one of is N; and / or R 1 , R 2 and R 3 At least one of the above comprises a structure of Formula VI, and L 6 For direct keys.

10. The compound according to claim 1, wherein R 1 , R 2 and R 3 At least one of the monovalent or multivalent forms comprises a structure selected from the group consisting of: Each R DD -R GG independently represents a single substitution to the maximum possible number of substitutions or no substitution; Each R DD -R GG and R N are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof; Where X 4 To X 27 Each independently is C or N; wherein A is selected from the group consisting of: B, N, P, PO, CR, SiR, GeR, Where L 1 -L 2 Each is independently selected from the group consisting of O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO2, SiRR', GeRR' and P(O)R.

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

12. The compound of claim 1, wherein the compound is selected from the group consisting of: wherein i is an integer from 469 to 575, and j, k, l and m are each independently an integer from 1 to 575, wherein R1 to R575 have the following structure:

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

14. An organic light emitting device (OLED), comprising: anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises formula R 1 R 2 R 3 ML-M' compounds; in M is Si or Ge; L is selected from the group consisting of direct bonds or from the group consisting of O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO2, SiRR', GeRR' and P(O)R; When L is a direct bond, M' is SiR 4 R 5 R 6 or GeR 4 R 5 R 6 ; When L is not a direct bond, M' is SiR 4 R 5 R 6 ,GeR 4 R 5 R 6 or one or more hydrocarbon groups, provided that at least one of the one or more hydrocarbon groups is a carbocyclic group; Each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; Any two substituents can be joined or fused to form a ring; R 1 , R 2 and R 3 at least one of which comprises a structure selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, and aza variants thereof; The conditions are: If L is a direct bond and both M and M' contain Si, then R 1 , R 2 and R 3 At least one of the following comprises benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim) or borane, or R 1 , R 2 and R 3 together form two structures selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole and aza variants thereof, with the additional proviso that the same R 1 , R 2 and R 3 Does not constitute dicarbazole; If M is Si, then R 1 , R 2 and R 3 At least two of them are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; If M' is SiR 4 R 5 R 6 , then R 4 , R 5 and R 6 At least two of are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; and The compounds contain no non-ring N atoms.

15. A consumer product comprising an organic light emitting device (OLED), the organic light emitting device comprising: anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises formula R 1 R 2 R 3 ML-M' compounds; in M is Si or Ge; L is selected from the group consisting of direct bonds or from the group consisting of: O, S, Se, BR, BRR', PR, CR, NR, C=O, C=S, C=NR, C=CRR', CRR', SO, SO2, SiRR', GeRR' and P(O)R; When L is a direct bond, M' is SiR 4 R 5 R 6 or GeR 4 R 5 R 6 ; When L is not a direct bond, M' is SiR 4 R 5 R 6 ,GeR 4 R 5 R 6 or one or more hydrocarbon groups, provided that at least one of the one or more hydrocarbon groups is a carbocyclic group; Each R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, boryl, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenoalkyl, and combinations thereof; Any two substituents can be joined or fused to form a ring; R 1 , R 2 and R 3 at least one of which comprises a structure selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole, and aza variants thereof; The conditions are: If L is a direct bond and both M and M' contain Si, then R 1 , R 2 and R 3 At least one of the following comprises benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim) or borane, or R 1 , R 2 and R 3 together form two structures selected from the group consisting of triphenylene, tetraphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, dibenzofluorene, benzo[d]benzo[4,5]imidazo[1,2-a]imidazole (bimbim), indolocarbazole, indolodibenzothiophene, indolodibenzofuran, indolodibenzoselenophene, indolodibenzofluorene, naphthalene, borane, pyridine, pyridazine, pyrimidine, pyrazine, triazine, imidazole, benzimidazole and aza variants thereof, with the additional proviso that the same R 1 , R 2 and R 3 Does not constitute dicarbazole; If M is Si, then R 1 , R 2 and R 3 At least two of them are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; If M' is SiR 4 R 5 R 6 , then R 4 , R 5 and R 6 At least two of are monocyclic or polycyclic structures comprising a 5-membered and / or 6-membered carbocyclic or heterocyclic ring which may be further substituted; and The compounds contain no non-ring N atoms.

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