CN115894449A - Spiro organic compound and application thereof in organic photoelectric device - Google Patents

Spiro organic compound and application thereof in organic photoelectric device Download PDF

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CN115894449A
CN115894449A CN202211466228.0A CN202211466228A CN115894449A CN 115894449 A CN115894449 A CN 115894449A CN 202211466228 A CN202211466228 A CN 202211466228A CN 115894449 A CN115894449 A CN 115894449A
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organic
compound
atoms
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spiro
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肖立清
杨曦
裘伟明
陈佳
艾田
李冬云
龙志飞
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Guangzhou Zhuoguang Technology Co ltd
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Abstract

The invention relates to a spiro organic compound and application thereof in an organic photoelectric device. The organic compound contains spiro and triazine structures, and can be used as an electron transport material to be applied to organic electronic devices, so that the luminous efficiency and the service life of the devices are effectively improved.

Description

Spiro organic compound and application thereof in organic photoelectric device
Technical Field
The invention relates to the field of photoelectric materials, in particular to a spiro organic compound and application thereof in an organic photoelectric device.
Background
Organic electroluminescent display devices are self-luminous display devices, which generate excitons by transfer and recombination of carriers between functional layers and emit light by means of organic compounds or metal complexes having high quantum efficiency. An organic electroluminescent element generally has a positive electrode and a negative electrode and an organic functional layer structure in between. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic functional layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, electrons are injected from the negative electrode into the organic functional layer, and when the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast and the like.
In order to improve the light emitting efficiency of the organic electroluminescent device, the development of an electron transport layer material is of great importance. Common electron transport materials such as AlQ 3 The electron mobility of (aluminum octahydroquinolinate) is much lowerThe hole mobility of the hole transport material can reduce the recombination probability of holes and electrons caused by the imbalance of injection and transport of carriers in the OLED device, thereby reducing the luminous efficiency of the device, and the electron transport material with lower electron mobility can increase the working voltage of the device, thereby affecting the power efficiency and being unfavorable for saving energy.
At present, although a large number of electron transport materials have been developed, the corresponding devices still have many problems such as unbalanced carrier transport and insufficient device lifetime. Chinese patent CN104541576A discloses a class of spiro derivatives used in electron transport layers of organic electronic devices, but the obtained device performance and lifetime need to be improved continuously.
Disclosure of Invention
The invention aims to provide a spiro organic compound serving as an electron transport material, which is applied to an organic photoelectric device and can effectively improve the efficiency and the service life of the device.
In order to realize the purpose of the invention, the provided specific solution technical scheme is as follows:
a spiro organic compound has a structural general formula shown in (I):
Figure BDA0003956353000000021
wherein;
z is independently selected from CR at each occurrence 0 Or N;
R 0 each occurrence is independently selected from-F, -Cl, -Br, -I, -CF 3 CN or NO 2 ；
R 1 、R 2 、R 3 At each occurrence, is independently selected from: -H, -D, straight chain alkyl having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cycloalkanyl having 3 to 20C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms, a heteroaromatic group having 5 to 30 ring atoms, or a combination thereof;
m is selected from 0, 1,2,3 or 4;
n is selected from 0, 1,2,3 or 4;
k is selected from 0, 1,2,3 or 4;
Ar 1 ～Ar 2 independently selected from substituted or unsubstituted aromatic group with 6-30 ring atoms and substituted or unsubstituted heteroaromatic group with 5-30 ring atoms.
Accordingly, the present invention also provides a mixture comprising at least the spiro organic compound as described above and at least one further organic functional material, wherein the at least one further organic functional material is selected from the group consisting of Hole Injection Material (HIM), hole Transport Material (HTM), electron Transport Material (ETM), electron Injection Material (EIM), electron Blocking Material (EBM), hole Blocking Material (HBM), luminescent material (Emitter), host material (Host) and organic dye.
Accordingly, the present invention also provides a composition comprising a spiro organic compound as described above, or a mixture of the above, and at least one organic solvent.
Correspondingly, the invention also provides an organic electronic device, wherein the functional layer comprises the spiro organic compound or the mixture, or is prepared from the composition.
Compared with the prior art, the invention has the remarkable advantages that:
1. the spiro organic compound provided by the invention has a specific substitution on a biphenyl group of a connecting group between a spiro and a triazine group in the structure, and the substituent has an electron withdrawing property, is favorable for electron injection, and can enhance the electron transport performance of the compound, particularly when Z is selected from CR 0 When the group is formed, the electron-withdrawing property of the compound is enhanced, the space structure of the compound is further optimized, the mobility and the stability of molecules are improved, and the prepared OLED device has longer service life and better external quantum efficiency;
2. the spiro organic compound provided by the invention can ensure that an organic electroluminescent device achieves the balance of carrier transmission through the specific substitution of specific sites, so that electrons and holes are compounded in the center of a luminescent layer, the quenching of excitons can be reduced, the luminous efficiency can be effectively improved, and the service life of the device can be prolonged.
Detailed Description
The described embodiments of the present invention are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention. In this application, unless stated to the contrary, the use of directional words such as "upper" and "lower" typically refer to upper and lower in the actual use or operating condition of the device. In addition, in the description of the present application, the terms "including" and "comprising" mean "including but not limited to," the terms "a plurality of" mean "two or more," and the terms "and/or" include any and all combinations of one or more of the associated listed items. Various embodiments of the present application may exist in a range of forms; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the stated range, such as 1,2,3,4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
The term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or/and", "and/or", it should be understood that, in the present application, the technical solutions definitely include the technical solutions all connected by "logic and", and also the technical solutions all connected by "logic or". For example, "A and/or B" includes three parallel schemes of A, B and A + B. For example, a reference to "a, and/or, B, and/or, C, and/or, D" includes any one of a, B, C, and D (i.e., all connected by "logical or"), any and all combinations of a, B, C, and D (i.e., any two or any three of a, B, C, and D), and any four combinations of a, B, C, and D (i.e., all connected by "logical and").
In the present invention, the aromatic groups, aromatic groups and aromatic ring systems have the same meaning and are interchangeable.
In the context of the present invention, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.
In the present invention, the "heteroatom" is a non-carbon atom, and may be a N atom, an O atom, an S atom or the like.
In the present invention, "substituted" means that one or more hydrogen atoms in a substituent are substituted with a substituent.
In the present invention, "mono-substituted" means substituted with one substituent, "di-substituted" means substituted with two substituents, "tri-substituted" means substituted with three substituents, "tetra-substituted" means substituted with four substituents, and "penta-substituted" means substituted with five substituents.
In the present invention, when the same substituent is present in plural times, it may be independently selected from different groups. If the general formula contains a plurality of R, R can be independently selected from different groups.
In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 20C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms, -NR' R ", silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted with art-acceptable substituents; understandably, R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 10C atoms, heterocyclic group containing 3 to 20 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group having 1 to 10C atoms, heterocyclic group having 3 to 10 ring atoms, aromatic group having 6 to 20 ring atoms, heteroaromatic group having 5 to 20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups may be further substituted with substituents acceptable in the art.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atom included in the substituent is not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
The "aryl group or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aryl group, or a condensed ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for a polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthenyl and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. <10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: thienyl, furyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-diazonaphthyl, phenanthridinyl, primidinyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing the term, e.g., "C 1 -C 9 Alkyl "means an alkyl group containing from 1 to 9 carbon atoms, which at each occurrence may be independently of each other C 1 Alkyl radical, C 2 Alkyl radical, C 3 Alkyl radical, C 4 Alkyl radical, C 5 Alkyl radical, C 6 Alkyl radical, C 7 Alkyl radical, C 8 Alkyl or C 9 An alkyl group. <xnotran> , , , , , , , ,2- ,3,3- , , , , , ,1- ,3- ,2- ,4- -2- , ,1- ,2- ,2- , ,4- ,4- , ,1- ,2,2- ,2- ,2- , , ,2- ,2- ,2- ,3,7- , , , , ,2- ,2- ,2- ,2- , , ,2- ,2- ,2- ,2- , , , , ,2- ,2- ,2- ,2- , , , , ,2- ,2- ,2- ,2- , </xnotran> N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like.
The term "alkoxy" refers to a group of the structure "-O-alkyl",i.e. an alkyl group as defined above is attached to other groups via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH) 3 or-OMe), ethoxy (-O-CH) 2 CH 3 or-OEt) and tert-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention, "-" attached to a single bond means a connection or fusion site;
in the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site;
in the present invention, when the same group contains a plurality of substituents of the same symbol, the substituents may be the same or different from each other, for example
Figure BDA0003956353000000051
The 6R's on the phenyl ring may be the same or different from each other.
In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example
Figure BDA0003956353000000052
Wherein R is attached to any substitutable site of the phenyl ring.
The terms "combination thereof", "any combination thereof", "combination of groups", "combination" and the like as used herein include all suitable combinations of any two or more of the listed groups.
In the present invention, "further", "still", "specifically", etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of the present invention.
In the present invention, "optionally", "optional" and "optional" refer to the presence or absence, i.e., to any one selected from the two juxtapositions "present" or "absent". If multiple optional parts appear in one technical scheme, if no special description exists, and no contradiction or mutual constraint relation exists, each optional part is independent.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
A spiro organic compound has a structural general formula shown as (I):
Figure BDA0003956353000000061
wherein;
each occurrence of Z is independently selected from CR 0 Or N;
R 0 each occurrence is independently selected from-F, -Cl, -Br, -I, -CF 3 -CN or-NO 2 ；
R 1 、R 2 、R 3 Each occurrence is independently selected from: -H, -D, straight chain alkyl having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cycloalkanyl having 3 to 20C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms, a heteroaromatic group having 5 to 30 ring atoms, or combinations thereof;
m is selected from 0, 1,2,3 or 4;
n is selected from 0, 1,2,3 or 4;
k is selected from 0, 1,2,3 or 4;
Ar 1 ～Ar 2 is independently selected from substituted or unsubstituted aromatic groups with 6 to 30 ring atoms and substituted or unsubstituted heteroaromatic groups with 5 to 30 ring atoms.
In one embodiment, Z is independently selected from N, C (CF) at each occurrence 3 )、C(CN)、CF。
Preferably, each occurrence of Z is selected from the same group.
Specifically, the general formula (I) is selected from any one of general formulas (II-1) to (II-4):
Figure BDA0003956353000000071
in the preferred embodimentIn, R 1 、R 2 、R 3 Each occurrence is independently selected from-H, -D, straight chain alkyl having 1 to 10C atoms, branched alkyl having 3 to 10C atoms, cycloalkanyl having 3 to 10C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 6 to 10 ring atoms, or a combination thereof.
In one embodiment, ar 1 ～Ar 2 Independently selected from a substituted or unsubstituted aromatic group having 6 to 15 ring atoms or a substituted or unsubstituted heteroaromatic group having 6 to 15 ring atoms.
Further, ar 1 ～Ar 2 Is independently selected from any one of the following (B-1) to (B-4) groups:
Figure BDA0003956353000000072
wherein:
x is independently selected from CR for each occurrence 4 Or N;
y is selected from O, S, NR 5 Or CR 6 R 7 ；
R 4 、R 5 、R 6 、R 7 Each occurrence is independently selected from-H, -D, straight chain alkyl having 1 to 20C atoms, branched chain alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms, or a heteroaromatic group having 5 to 30 ring atoms, or combinations thereof.
When X is a linking site, X is selected from a C atom; when Y is selected from the attachment sites, Y is selected from the N atom.
Further, ar 1 ，Ar 2 Independently selected from any one of the groups of the general formulas (C-1) to (C-9):
Figure BDA0003956353000000081
in a preferred embodiment, R 4 、R 5 、R 6 、R 7 Each occurrence is independently selected from-H, -D, straight chain alkyl having 1 to 10C atoms, branched chain alkyl having 3 to 10C atoms, cyclic alkyl having 3 to 10C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 10 ring atoms, or a heteroaromatic group having 6 to 10 ring atoms, or combinations thereof.
The spiro organic compounds according to the present invention are selected from the following structures without being limited thereto:
Figure BDA0003956353000000082
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Figure BDA0003956353000000091
/>
Figure BDA0003956353000000101
/>
Figure BDA0003956353000000111
/>
Figure BDA0003956353000000121
wherein: h in the above structure may be further optionally substituted.
The invention further relates to an electron transport layer material selected from the spiro organic compounds described above.
The spiro organic compound according to the present invention can be used as a functional material in a functional layer of an organic electronic device. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).
Preferably, the spiro organic compounds according to the present invention are used in organic electronic devices as electron transport materials.
The invention further relates to a mixture comprising at least one spiro organic compound as described above, and at least one further organic functional material, which may be selected from the group consisting of Hole Injection Materials (HIM), hole Transport Materials (HTM), electron Transport Materials (ETM), electron Injection Materials (EIM), electron Blocking Materials (EBM), hole Blocking Materials (HBM), luminescent materials (Emitter), host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example in WO2015152650A1, the entire contents of which are hereby incorporated by reference.
In one embodiment, the further organic functional material is selected from hole transport materials, which are used as co-hosts in organic electronic devices.
The invention also relates to a composition comprising at least one spiro organic compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.
In a preferred embodiment, a composition according to the invention, said at least one organic solvent is chosen from aromatic-or heteroaromatic-based solvents.
Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, alpha, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, etc.;
examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;
examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxy-benzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;
in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchyne, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.
The solvents mentioned may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the present invention comprises at least one spiro organic compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δ d (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0 MPa1/2;
δ p (polar force) is in the range of 0.2 to 12.5MPa1/2, particularly in the range of 2.0 to 6.0 MPa1/2;
delta h (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, particularly in the range of 2.0 to 6.0 MPa1/2.
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.
In a preferred embodiment, the composition according to the invention is a solution.
In another preferred embodiment, the composition according to the invention is a suspension.
The compositions of the embodiments of the present invention may comprise from 0.01 to 10wt%, preferably from 0.1 to 15wt%, more preferably from 0.2 to 5wt%, most preferably from 0.25 to 3wt% of the spiro organic compound or mixture according to the present invention.
The invention also relates to the use of said composition as a coating or printing ink for producing organic electronic components, particularly preferably by printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, improving adhesion, and the like. For details on printing techniques and their requirements for solutions, such as solvent and concentration, viscosity, etc., see the printed media handbook, edited by Helmut Kipphan: techniques and Production Methods (Handbook of Print Media: technologies and Production Methods), ISBN 3-540-67326-1.
The present invention also provides the use of a spiro Organic compound, mixture or composition as described above in an Organic electronic device, which may be selected from, but not limited to, organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), organic light Emitting cells (OLEECs), organic Field Effect Transistors (OFETs), organic light Emitting field effect transistors (OFETs), organic lasers, organic spintronic devices, organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., and particularly preferably is an OLED. In the embodiment of the present invention, the spiro organic compound is preferably used for an electron transport layer of an OLED device.
The invention further relates to an organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers located between the first electrode and the second electrode, said organic functional layers comprising a spiro organic compound, a mixture or being prepared from a composition as described above. Further, the organic electronic device comprises a cathode, an anode and one or more organic functional layers positioned at the cathode and the anode.
The Organic electronic device can be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (oelt), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like, and particularly preferred is an Organic electroluminescent device such as an OLED, OLEEC, or an Organic light Emitting field effect transistor.
The organic functional layer according to the present invention may be selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are listed above. Various organic functional materials are described in detail, for example in WO2015152650A1, the entire contents of which are hereby incorporated by reference.
In one embodiment, the organic functional layer comprises an electron transport layer comprising the spiro organic compound described above. The definition of the specific spiro organic compound is as described above.
In one embodiment, an organic electronic device according to the present invention comprises a cathode, an anode, a light-emitting layer between the cathode and the anode, and an electron transport layer between the anode and the light-emitting layer.
Further, the organic electronic device according to the present invention comprises a cathode, an anode, a light emitting layer between the cathode and the anode, a hole transport layer between the anode and the light emitting layer, and an electron transport layer between the cathode and the light emitting layer.
Further, the organic electronic device further comprises a hole injection layer positioned between the anode and the hole transport layer.
Further, the organic electronic device further comprises an electron injection layer positioned between the cathode and the electron transport layer.
Further, the organic electronic device further comprises an electron blocking layer positioned between the hole transport layer and the light emitting layer.
In particular, the substrate may be transparent or opaque. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, bulovic et al Nature 1996,380, p29, and Gu et al appl. Phys. Lett.1996,68, p2606. The substrate may also be rigid or elastic. In one embodiment, the substrate is plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a small surface roughness and no surface defects. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 ℃ or higher, preferably above 200 ℃, more preferably above 250 ℃, and most preferably above 300 ℃. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode is an electrode for injecting holes, and the anode can efficiently inject holes into the hole injection layer, or the hole transport layer, or the light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. Examples of anode materials include, but are not limited to: al, cu, au, ag, mg, fe, co, ni, mn, pd, pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable known anode materials can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) assisted evaporation, and the like. In certain embodiments, the anode is pattern structured. The patterned ITO conductive substrate may be obtained by conventional etching methods such as laser etching or photoresist etching, and may be used to fabricate devices according to the present application.
The cathode is an electrode for injecting electrons, and the cathode can efficiently inject electrons into the electron injection layer, or the electron transport layer, or the light emitting layer. The cathode may comprise a conductive metal or conductive metal oxide. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light emitting layer or the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. In principle, all materials which can be used as cathodes for organic electronic devices are possible as cathode materials for organic electronic devices according to the present application. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy, baF2/Al, cu, fe, co, ni, mn, pd, pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) assisted evaporation, and the like.
The hole injection layer is a layer for promoting injection of holes from the anode to the light-emitting layer, the hole injection material is a material that can efficiently receive holes injected from the positive electrode at a low voltage, and it is preferable that the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Common hole injection materials include, but are not limited to: metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile-hexaazatriphenylene-based organic materials, and the like.
The hole transport layer can efficiently receive holes injected from the anode or the hole injection layer and transport the holes to the light emitting layer. Common hole transport materials include, but are not limited to: aromatic amine compounds, styrene compounds, butadiene compounds, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto.
The electron blocking layer may be disposed between the hole transport layer and the light emitting layer for blocking transport of electrons from the light emitting layer to the hole transport layer. Common electron blocking layer materials include, but are not limited to: triarylamine organic compounds, bicarbazole compounds, or materials known in the art.
The light emitting layer may emit red, green or blue light, and may be composed of a phosphorescent material or a fluorescent material. The light emitting material may receive holes and electrons from the hole transport layer and the electron transport layer, respectively, combine the holes and the electrons in the light emitting layer to emit light corresponding thereto, and is preferably a fluorescent or phosphorescent material having good quantum efficiency for fluorescence or phosphorescence.
Examples of the host material for the light-emitting layer include a condensed aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specifically, examples of the fused aromatic ring derivative include an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and examples of the heterocycle-containing compound include a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, but examples thereof are not limited thereto.
For the light-emitting layer to emit red light, the following can be used as a light-emitting guest material: phosphorescent materials such as bis (1-phenylisoquinoline) iridium acetylacetonate (PIQIr (acac)), bis (1-phenylquinoline) iridium acetylacetonate (PQIr (acac)), tris (1-phenylquinoline) iridium (PQIr), or platinum octaethylporphyrin (PtOEP); or a fluorescent material such as tris (8-hydroxyquinoline) aluminum (Alq 3), but is not limited thereto. In order to make the light emitting layer emit green light, a phosphorescent material such as tris (2-phenylpyridine) iridium (Ir (ppy) 3), GD1, or a fluorescent material such as tris (8-hydroxyquinoline) aluminum (Alq 3) may be used as a light emitting dopant, but is not limited thereto. For the light-emitting layer to emit blue light, the following may be used as a light-emitting dopant: phosphorescent materials, such as (4,6-F2 ppy) 2Irpic; or a fluorescent material such as spiro-DPVBi, spiro-6P, distyrylbenzene (DSB), distyrylarylene (DSA), pyrene-based arylamine compound, boron nitrogen compound, PFO-based polymer or PPV-based polymer, but not limited thereto.
The electron injection layer can facilitate the injection of electrons from the negative electrode and reduce the voltage required for the injection, and specific examples thereof include, but are not limited to: fluorenones, anthraquinone dimethanes, diphenoquinones, thiopyran dioxides, oxazoles, diazoles, triazoles, imidazoles, perylene tetracarboxylic acids, fluorenylidene methanes, anthrones, and the like and derivatives thereof, metal complex compounds such as LiQ, nitrogen-containing 5-membered ring derivatives, tmPyPB, and the like.
The organic electronic device emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.
In one embodiment, the organic functional layer comprises an electron transport layer comprising the spiro organic compound described above.
The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The present invention will be described in connection with the following examples of the preparation of compounds, but the present invention is not limited to the following examples, and it will be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit and scope of the invention.
Preparation of the compound:
example 1: synthesis of Compound 3
Figure BDA0003956353000000171
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Synthesis of Compound 1-1
Accurately weighing a compound B-9,9' -spirobifluorene-2 ' -yl boric acid (36g, 100mmol), 3, 5-dibromopyridine (23.7g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the compound B, the spirobifluorene-2 ' -yl boric acid, the 3, 5-dibromopyridine (23.7g, 100mmol), the tetratriphenylphosphine palladium (1.2g, 1mmol) and the potassium carbonate into a 1000mL three-neck flask, adding 500mL of dioxane and 100mL of water, pumping through nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, stirring a silica gel sample, carrying out column chromatography, and obtaining a compound 1-1 about 38.6g with an eluent of PE: EA =8 (volume ratio). Yield 81.7%: ms:473.07
Synthesis of Compounds 1-2:
accurately weighing the compound 1-1 (37.9g, 80mmol), the pinacol ester bisboronic acid (30.5g, 120mmol) and the ferrocene palladium dichloride (0.6 g) and the potassium acetate (15.7g, 160mmol) which are sequentially added into a 1000mL three-neck flask, about 600mL of anhydrous dioxane is added, nitrogen is pumped in for three times, and then the temperature is raised to 100 ℃ for reaction for 4 hours. And (3) after the raw materials completely react, cooling to room temperature, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and obtaining a compound 1-2 about 33.6g by using an eluent as PE: DCM =5 (volume ratio). The yield thereof was found to be 80.9%. Ms 520.49 synthesis of compounds 1-3:
accurately weighing compound A (42g, 100mmol), 5-bromopyridine-3-boric acid (20.2g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6 g, 200mmol) in turn, adding 500mL of dioxane and 100mL of water into a 1000mL three-neck flask, pumping nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting for three times with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample mixing and column chromatography, and eluting with PE: EA =8 (volume ratio) to obtain about 43.2g of compound 1-3. Yield 79.8%: ms:542.24 Synthesis of Compound 3:
accurately weighing compounds 1-3 (5.4g, 10mmol), compounds 1-2 (5.2g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL water, pumping nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel dressing column chromatography, and eluting with PE: EA =8 (volume ratio), thus obtaining about 6.3g of compound. Yield 73.8%: ms:854.84
Example 2: synthesis of Compound 9
Figure BDA0003956353000000181
Synthesis of Compound 2-1:
accurately weighing the compound B (44.6 g, 100mmol), 5-bromopyridine-3-boric acid (20.2 g, 100mmol), tetratriphenylphosphine palladium (1.2 g, 1mmol) and potassium carbonate (27.6 g, 200mmol) in sequence, adding 500mL of dioxane and 100mL of water into a 1000mL three-neck flask, pumping and filling nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, mixing silica gel with a sample, and eluting with EA =8 (volume ratio) to obtain the compound 2-1 of about 41.2g. Yield 72.6%: ms:568.31 Synthesis of compound 9:
accurately weighing compound 2-1 (5.7g, 10mmol), compound 1-2 (5.2g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL of water, pumping and charging nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and eluting with PE: EA =8 (volume ratio), thus obtaining compound 9 of about 6.5g. Yield 73.8%: ms:880.90
Example 3: synthesis of Compound 22
Figure BDA0003956353000000182
Synthesis of Compound 3-1:
accurately weighing compound C (36.8g, 100mmol), 5-bromopyridine-3-boric acid (20.2g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 500mL dioxane and 100mL water, pumping and introducing nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, stirring silica gel for column chromatography, and eluting with PE: EA =8 (volume ratio), thus obtaining about 36.6g of compound 3-1. Yield 74.8%: ms:490.03 Synthesis of compound 22:
accurately weighing the compound 3-1 (4.9g, 10mmol), the compound 1-2 (5.2g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL of water, pumping nitrogen gas, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, and eluting with PE: EA =8 (volume ratio), so as to obtain about 5.5g of the compound 22. Yield 68.6%: ms:802.73
Example 4: synthesis of Compound 33
Figure BDA0003956353000000191
Synthesis of Compound 4-1
Accurately weighing the compound B-9,9 '-spirobifluorene-2' -yl boric acid (36g, 100mmol), 3, 5-dibromofluorobenzene (25.4 g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6 g, 200mmol) and sequentially adding the materials into a 1000mL three-neck flask, adding 500mL of dioxane and 100mL of water, pumping nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then removing redundant solvent by reduced pressure distillation, mixing silica gel with a sample, performing column chromatography, wherein the eluent is PE: EA =8 (volume ratio), yielding about 38.6g of compound 4-1. Yield 78.9%: ms:490.25
Synthesis of Hua Compound 4-2:
accurately weighing the compound 4-1 (29.4g, 60mmol), the pinacol ester bisboronic acid (30.5g, 120mmol) and the ferrocene palladium dichloride (0.6 g) and the potassium acetate (15.7g, 160mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding about 600mL of anhydrous dioxane, pumping and charging nitrogen for three times, and then heating to 100 ℃ for reaction for 4 hours. And (3) after the raw materials completely react, cooling to room temperature, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and obtaining a compound 4-2 of about 33.6g by using an eluent as PE: DCM =5 (volume ratio). The yield thereof was found to be 62.6%. Ms 537.31 synthesis of compounds 4-3:
accurately weighing compounds 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (26.7g, 100mmol), 5-bromo-3-fluorobenzeneboronic acid (21.9g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the compounds into a 1000mL three-neck flask, adding 400mL dioxane and 80mL water, pumping and charging nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying anhydrous sodium sulfate, decompressing and distilling to remove redundant solvent, carrying out silica gel column chromatography for sample mixing, and eluting with a eluent PE: EA =8 (volume ratio), thus obtaining 4-3 about 26.7g of the compound. Yield 65.7%: ms:407.09
Synthesis of compound 33:
accurately weighing compounds 4-3 (4.1g, 10mmol), compounds 4-2 (5.4g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL water, pumping nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel dressing column chromatography, and eluting with PE: EA =8 (volume ratio), thereby obtaining a compound 33 of about 5.5g. Yield 74.7%: ms:736.53
Example 5: synthesis of Compound 52
Figure BDA0003956353000000201
Synthesis of Compound 5-1:
accurately weighing compounds 2-chloro-4- (4-biphenyl) yl-6- (2-naphthalene) yl-1, 3, 5-triazine (39.4g, 100mmol), 5-bromo-3-fluorobenzeneboronic acid (21.9g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol) in turn, adding 400mL of dioxane and 80mL of water into a 1000mL three-neck flask, pumping nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting for three times with ethyl acetate, combining organic phases, drying anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, carrying out silica gel sample stirring and column chromatography, wherein an eluent is PE: EA =8 (volume ratio), and obtaining about 37.8g of the compound 5-1. Yield 71%: ms:533.21
Synthesis of compound 52:
accurately weighing the compound 5-1 (5.3g, 10mmol), the compound 4-2 (5.4g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL of water, pumping nitrogen gas, heating to 90 ℃ for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water to dilute, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, wherein the eluent is PE: EA =8 (volume ratio), and obtaining about 5.6g of the compound 52. Yield 68.3%: ms:863.11
Example 6: synthesis of Compound 54
Figure BDA0003956353000000202
Synthesis of Compound 6-1:
accurately weighing a compound C (36.8g, 100mmol), 5-bromo-3-fluorobenzeneboronic acid (21.9g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol) in turn, adding 400mL of dioxane and 80mL of water into a 1000mL three-neck flask, pumping and introducing nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, stirring with silica gel, eluting with a PE: EA =8 (volume ratio), and carrying out column chromatography to obtain 6-1 about 35.5g of the compound C. Yield 70.1%: ms:507.26 Synthesis of compound 54:
accurately weighing 6-1 (5.1g, 10mmol) compounds, 4-2 (5.4g, 10mmol) tetratriphenylphosphine palladium (0.12g, 0.10mmol) compounds and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL water, pumping nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel dressing column chromatography, and eluting with PE: EA =8 (volume ratio) to obtain 54.8 g compounds. Yield 69.4%: ms:836.74
Example 7: synthesis of Compound 70
Figure BDA0003956353000000211
Synthesis of Compound 7-1
Accurately weighing a compound B-9,9 '-spirobifluorene-2' -yl boric acid (36g, 100mmol), 3, 5-dibromobenzonitrile (26.1g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the compound B-9,9 '-spirobifluorene-2' -yl boric acid, the compound B-5, the compound B-9, the compound B-5, the compound B-dibromobenzonitrile (26.1g, 100mmol) and the tetratriphenylphosphine palladium (1.2g, 1mmol) into a 1000mL three-neck flask, adding 500mL dioxane and 100mL of water, pumping and introducing nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, carrying out silica gel sample-mixing column chromatography, wherein an eluent is PE: EA =8 (volume ratio) to give about 34.6g of compound 7-1. Yield 69.7%: ms:497.06
Synthesis of Compound 7-2:
accurately weighing the compound 6-1 (29.8g, 60mmol), the pinacol ester bisboronic acid (30.5g, 120mmol) and the ferrocene palladium dichloride (0.6 g) potassium acetate (15.7g, 160mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding about 600mL of anhydrous dioxane, pumping nitrogen gas, charging three times, and raising the temperature to 100 ℃ for reaction for 4 hours. And (2) after the raw materials completely react, cooling to room temperature, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, and then distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, wherein the eluent is PE: DCM =5 (volume ratio), and obtaining about 34.3g of the compound-2. The yield thereof was found to be 63.1%. Ms 544.25 synthesis of compound 7-3:
accurately weighing compound D (35.8g, 100mmol), 5-bromo-3-cyanoboronic acid (22.6g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 400mL dioxane and 80mL water, pumping and introducing nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, stirring silica gel for column chromatography, and eluting with PE: EA =8 (volume ratio) to obtain 7-3 about 29.8g of compound. Yield 59.2%: ms:504.09 Synthesis of compound 70:
accurately weighing compounds 7-3 (5g, 10mmol), compounds 7-2 (5.4g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.12mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL water, pumping nitrogen gas, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvents, carrying out silica gel stirring and column chromatography, and obtaining a compound 70 of about 5.7g, wherein the eluent is PE: EA = 8. Yield 67.9%: ms:840.88
Example 8: synthesis of Compound 85
Figure BDA0003956353000000221
Synthesis of Compound 8-1:
accurately weighing the compound C (36.8g, 100mmol), 5-bromo-3-cyanophenylboronic acid (21.9g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol) into a 1000mL three-neck flask, adding dioxane 400mL and water 80mL, pumping nitrogen gas, raising the temperature to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, mixing silica gel with a sample, performing column chromatography, and eluting with EA =8 (volume ratio) to obtain the compound 8-1 of about 35.5g. Yield 69.1%: ms:514.31 Synthesis of compound 54:
accurately weighing the compound 8-1 (5.1g, 10mmol), the compound 7-2 (5.4g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL of water, pumping nitrogen gas, heating to 90 ℃ for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water to dilute, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, wherein the eluent is PE: EA =8 (volume ratio), and obtaining about 5.8g of the compound 85. Yield 68.2%: ms:851.02
Example 9: synthesis of Compound 93
Figure BDA0003956353000000222
Synthesis of Compound 9-1
Accurately weighing the compound B-9,9 '-spirobifluorene-2' -yl boric acid (36g, 100mmol), 3, 5-dibromotrifluorotoluene (30.4 g, 100mmol), palladium tetratriphenylphosphine (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol) in sequence, adding 500mL of dioxane and 100mL of water, pumping through nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying anhydrous sodium sulfate, removing excessive solvent by reduced pressure distillation, carrying out silica gel stirring and column chromatography, wherein the eluent is PE: EA =8 (volume ratio), and obtaining about 34.4g of the compound 9-1. Yield 63.8%: ms:540.41
Synthesis of Compound 9-2:
accurately weighing the compound 9-1 (32.4g, 60mmol), the pinacol ester bisboronic acid (30.5g, 120mmol) and the ferrocene palladium dichloride (0.6 g) and the potassium acetate (15.7g, 160mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding about 600mL of anhydrous dioxane, pumping and charging nitrogen for three times, and then heating to 100 ℃ for reaction for 4 hours. And (2) after the raw materials completely react, cooling to room temperature, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, and then distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, wherein the eluent is PE: DCM =5 (volume ratio), and obtaining about 35.1g of the compound 9-2. The yield thereof was found to be 59.9%. Ms:587.32 Synthesis of Compounds 9-3:
accurately weighing compounds 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (35.8g, 100mmol), 5-bromo-3-trifluoromethylphenylboronic acid (26.9g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding into a 1000mL three-neck flask, adding 400mL dioxane and 80mL water, pumping and charging nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, removing the redundant column chromatography solvent by reduced pressure distillation, stirring with silica gel, and eluting with PE: EA =8 (volume ratio) to obtain about 27.8g of a compound 9-3. Yield 60.9%: ms:457.06
Synthesis of compound 93:
accurately weighing the compound 9-3 (4.6 g, 10mmol), the compound 9-2 (5.9g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL of water, pumping and charging nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and eluting with PE: EA =8 (volume ratio), thereby obtaining the compound 93 of about 5.7g. Yield 67.9%: ms:836.67
Example 10: synthesis of Compound 105
Figure BDA0003956353000000231
Synthesis of Compound 10-1:
accurately weighing compound M (37.4g, 100mmol), 5-bromo-3-trifluoromethylphenylboronic acid (22.6g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 400mL dioxane and 80mL of water, pumping through nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, and eluting with PE: EA =8 (volume ratio), thus obtaining compound 10-1 of about 31.6g. Yield 56.2%: ms:563.37
Synthesis of compound 105:
accurately weighing 10-1 (5.6 g, 10mmol) of a compound, 9-2 (5.9g, 10mmol) of tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL of dioxane and 20mL of water, pumping and introducing nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, wherein an eluting agent is PE: EA =8 (volume ratio), and obtaining about 6.1g of the compound 105. Yield 64.8%: ms:942.95
Example 11: synthesis of Compound 134
Figure BDA0003956353000000241
Synthesizing a compound 11-1;
accurately weighing 2, 7-dibromo-9, 9' -spirobifluorene (47.4g, 100mmol), deuterated phenylboronic acid (12.7g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 400mL of dioxane and 80mL of water, pumping and charging nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and obtaining a compound 11-1 of about 31.6g, wherein the eluent is PE: EA =8 (volume ratio). Yield 66.3%: ms:477.35
Synthesis of Compound 11-2:
accurately weighing the compound 11-1 (28.6 g, 60mmol), 5-bromopyridine-3-boric acid (12.1g, 60mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (16.6 g, 120mmol), sequentially adding the tetrakistriphenylphosphine palladium (1.2g, 1mmol) and the potassium carbonate into a 1000mL three-neck flask, adding 500mL dioxane and 100mL water, pumping through nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring and column chromatography, and obtaining the compound 11-2 of about 25.3g, wherein the eluent is PE: EA = 8. Yield 76.2%: ms:554.43 Synthesis of Compounds 11-4:
accurately weighing the compound 11-3 (35.8g, 100mmol), 5-bromopyridine-3-boric acid (20.2g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 500mL dioxane and 100mL water, pumping nitrogen gas, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, mixing silica gel with a sample column, and obtaining about 35.3g of the compound 11-4, wherein the volume ratio of the eluent is PE: EA = 8. Yield 73.6%: ms: 480.21.
synthesis of Compounds 11-5:
accurately weighing the compounds 11-4 (28.8g, 60mmol), the pinacol ester bisboronic acid (30.5g, 120mmol) and the ferrocene palladium dichloride (0.6 g) potassium acetate (15.7g, 160mmol), sequentially adding the components into a 1000mL three-neck flask, adding about 600mL of anhydrous dioxane, pumping nitrogen gas, charging three times, and raising the temperature to 100 ℃ for reaction for 4 hours. Cooling the raw materials to room temperature after complete reaction, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample stirring column chromatography, and obtaining a compound 11-5 about 23.4g by using an eluent as PE: DCM = 5. The yield thereof was found to be 74.1%. Ms 527.37
Synthesis of compound 134:
accurately weighing 11-2 (5.5g, 10mmol) compounds, 11-5 (5.3g, 10mmol) tetratriphenylphosphine palladium (0.12g, 0.10mmol) compounds and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL heavy water, pumping and charging nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and eluting with PE: EA =8 to obtain about 5.3g compounds, wherein the weight of the compound is determined by the following steps of. Yield 60.7%: ms:873.88
Example 12: compound 135
Figure BDA0003956353000000251
Synthesis of Compound 12-1:
accurately weighing the compounds 2, 4-bis (4-tert-butylphenyl) -6-chloro-1, 3, 5-triazine (38g, 100mmol), 5-bromo-3-cyanoboronic acid (22.6 g, 100mmol), tetratriphenylphosphine palladium (1.2 g, 1mmol) and potassium carbonate (27.6 g, 200mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding 500mL dioxane and 100mL water, pumping nitrogen for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, removing redundant solvent by reduced pressure distillation, carrying out silica gel sample mixing and column chromatography, wherein an eluent is PE: EA =8 (volume ratio), and obtaining 12-1 about 38.2g of the compound. Yield 72.7%: ms:526.38
Synthesis of Compound 12-2:
accurately weighing the compound 12-1 (31.5g, 60mmol), pinacol bisboronic acid ester (30.5g, 120mmol) and ferrocene palladium dichloride (0.6 g) potassium acetate (15.7g, 160mmol), sequentially adding the mixture into a 1000mL three-neck flask, adding about 600mL of anhydrous dioxane, pumping and charging nitrogen for three times, and then heating to 100 ℃ for reaction for 4 hours. And after the raw materials completely react, cooling to room temperature, adding water for dilution, extracting for three times by ethyl acetate, combining organic phases, drying by anhydrous sodium sulfate, then distilling under reduced pressure to remove redundant solvent, carrying out silica gel sample stirring column chromatography, and obtaining a compound 12-2 about 23.4g by using an eluent as PE: DCM = 5. The yield thereof was found to be 68.1%. Ms 573.45
Synthesis of Compounds 12-3:
accurately weighing 2-bromo-2, 7-di-tert-butyl-9, 9-spirobifluorene (50.8g, 100mmol), 5-bromo-3-cyanobenzoic acid (22.6g, 100mmol), tetratriphenylphosphine palladium (1.2g, 1mmol) and potassium carbonate (27.6g, 200mmol) sequentially into a 1000mL three-neck flask, adding 400mL dioxane and 80mL water, pumping in nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials are completely reacted, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, removing the excessive solvent by reduced pressure distillation, stirring with silica gel, and obtaining about 38.6g of a compound 12-3, wherein the eluent is PE: EA = 8. Yield 63.4%: ms:609.34
Synthesis of compound 135:
accurately weighing compound 12-3 (6.1g, 10mmol), compound 12-2 (5.7g, 10mmol), tetratriphenylphosphine palladium (0.12g, 0.10mmol) and potassium carbonate (2.8g, 20mmol) into a 250mL three-neck flask, adding 10mL dioxane and 20mL heavy water, pumping and charging nitrogen gas for three times, heating to 90 ℃ for reaction for 6 hours, cooling to room temperature after the raw materials completely react, adding water for dilution, extracting with ethyl acetate for three times, combining organic phases, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove redundant solvent, carrying out silica gel stirring column chromatography, and eluting with PE: EA =8 to obtain about 5.5g of compound 135. Yield 56.5%: ms:975.28
Preparing a device:
the preparation of an OLED device comprising the above compound is described in detail below by means of specific examples.
The device 1 is prepared as follows:
(1) And cleaning the ITO conductive glass anode layer by using a detergent, cleaning the ITO conductive glass anode layer by using deionized water, acetone and isopropanol for 15 minutes, blow-drying the ITO conductive glass anode layer by using nitrogen, and treating the ITO conductive glass anode layer in a plasma cleaner for 5 minutes to improve the work function of the electrode.
(2) Transferring the ITO conductive glass substrate into a vacuum vapor deposition device under high vacuum (1 × 10) -6 Mbar), steamingAnd plating a hole injection layer material HATCN with the thickness of 5nm.
(3) On the hole injection layer, a high vacuum (1X 10) is applied -6 Mbar) was evaporated to a thickness of 80nm to form a hole transport layer.
(4) And (2) evaporating a light-emitting layer on the hole transport layer, selecting GH1 as a host material and GD1 as a doping material, wherein the mass ratio of GD1 to GH1 is 1.
(5) High vacuum (1X 10) on the light-emitting layer -6 Mbar) evaporated compound 3 formed an electron transport layer of 25 nm.
(6) High vacuum (1X 10) on the electron transport layer -6 Mbar) was thermally evaporated to form an electron injection layer with a thickness of 1 nm.
(7) On the electron injection layer, high vacuum (1X 10) -6 Mbar) evaporated metal Al to a thickness of 100nm to form a cathode.
(8) The devices were encapsulated with uv curable resin in a nitrogen glove box.
In the preparation of the device, the evaporation rate of the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer and the electron injection layer is as follows
Figure BDA0003956353000000271
The evaporation rate of the cathode layer is->
Figure BDA0003956353000000272
Device example 2: the compound 9 is used as an electron transport layer material of an organic electroluminescent device, and the compound 3 in the device example 1 is replaced, and other conditions are not changed.
Device example 3: the compound 22 for the electron transport layer material of the organic electroluminescent device is used for replacing the compound 3 in the device example 1, and other conditions are not changed.
Device example 4: the compound 33 for the electron transport layer material of the organic electroluminescent device was used in place of the compound 3 in device example 1, and the other conditions were not changed.
Device example 5: the compound 52 for the electron transport layer material of the organic electroluminescent device is used for replacing the compound 3 in the device example 1, and other conditions are not changed.
Device example 6: the compound 54 for the electron transport layer material of the organic electroluminescent device was used in place of the compound 3 in device example 1, and the other conditions were not changed.
Device example 7: the compound 70 for the electron transport layer material of the organic electroluminescent device was used in place of the compound 3 in device example 1, and the other conditions were not changed.
Device example 8: the compound 85 is used as an electron transport layer material of an organic electroluminescent device to replace the compound 3 in the device example 1, and other conditions are not changed.
Device example 9: the compound 93 is used as the material of the electron transport layer of the organic electroluminescent device, and the compound 3 in the embodiment 1 is replaced by the compound, and other conditions are not changed.
Device example 10: the compound 105 for the electron transport layer material of the organic electroluminescent device replaces the compound 3 in the device example 1, and other conditions are not changed.
Device example 11: the compound 134 for the electron transport layer material of the organic electroluminescent device was used in place of the compound 3 in device example 1, and the other conditions were not changed.
Device example 12: the compound 135 for the material of the electron transport layer of the organic electroluminescent device was used in place of the compound 3 in device example 1, and the other conditions were not changed.
Comparative example 1: ref is used as an electron transport layer material of the organic electroluminescent device to replace the compound 3 in the device example 1, and other conditions are not changed.
The structures of the compounds involved in the devices are as follows:
Figure BDA0003956353000000273
Figure BDA0003956353000000281
ref synthesis is described in WO2016105141A.
The current-voltage (J-V) characteristics of the organic light emitting diodes of device examples 1-8 and comparative example 1 were tested using a characterization apparatus while recording important parameters such as lifetime and external quantum efficiency. The external quantum efficiency is that the current density is 10mA/cm 2 The relative value obtained here, LT95@1000nits, is the time for the luminance to drop from the initial luminance of 1000nits to 95% of the initial luminance at a constant current. All external quantum efficiencies and lifetimes are relative values with respect to the organic light emitting diode of comparative example 1, i.e. with a lifetime lt95@1000nits of comparative example 1 of 1, the external quantum efficiency EQE of 1.
TABLE 1
Numbering Electron transport layer material External quantum efficiency (relative value) LT95@1000nits
Device example 1 Compound 3 1.09 1.08
Device example 2 Compound 9 1.07 1.05
Device example 3 Compound 22 1.06 1.02
Device example 4 Compound 33 1.10 1.12
Device example 5 Compound 52 1.15 1.09
Device example 6 Compound 54 1.13 1.11
Device example 7 Compound 70 1.12 1.15
Device example 8 Compound 85 1.14 1.11
Device example 9 Compound 93 1.12 1.14
Device example 10 Compound 105 1.16 1.14
Device example 11 Compound 134 1.11 1.07
Device example 12 Compound 135 1.13 1.12
Comparative example 1 Compound Ref1 1 1
From table 1 it can be seen that the compounds of the invention produce OLED devices with longer lifetime and better external quantum efficiency than comparative example 1, because: by specific substitution on the biphenyl group, the linking group between the spiro ring and the triazine group, the substituent has electron withdrawing property, is beneficial to electron injection, and can enhance the electron transport performance of the compound, particularly when Z is selected from CR 0 In the process, the electron-withdrawing property of the compound is enhanced, the space structure of the compound is further optimized, the mobility and the stability of molecules are improved, and therefore the efficiency and the service life of the device are remarkably improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A spiro organic compound characterized by: the general structural formula is shown as (I):
Figure FDA0003956352990000011
wherein;
each occurrence of Z is independently selected from CR 0 Or N;
R 0 each occurrence is independently selected from-F, -Cl, -Br, -I, -CF 3 CN or NO 2 ；
R 1 、R 2 、R 3 Each occurrence is independently selected from: -H, -D, straight chain alkyl having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, cycloalkanyl having 3 to 20C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms, a heteroaromatic group having 5 to 30 ring atoms, or a combination thereof;
m is selected from 0, 1,2,3 or 4;
n is selected from 0, 1,2,3 or 4;
k is selected from 0, 1,2,3 or 4;
Ar 1 ～Ar 2 independently selected from substituted or unsubstituted aromatic group with 6-30 ring atoms and substituted or unsubstituted heteroaromatic group with 5-30 ring atoms.
2. A spiro organic compound according to claim 1, wherein: in the general formula (I), each occurrence of Z is independently selected from N and C (CF) 3 )、C(CN)、CF。
3. A spiro organic compound according to claim 1, wherein: the general formula (I) is selected from any one of general formulas (II-1) to (II-4):
Figure FDA0003956352990000012
Figure FDA0003956352990000021
4. a spiro organic compound according to claim 1, wherein: ar (Ar) 1 ～Ar 2 Is independently selected from any one of the following (B-1) to (B-4) groups:
Figure FDA0003956352990000022
wherein:
x is independently selected from CR at each occurrence 4 Or N;
y is selected from O, S, NR 5 Or CR 6 R 7 ；
R 4 、R 5 、R 6 、R 7 Each occurrence is independently selected from-H, -D, straight chain alkyl having 1 to 20C atoms, branched chain alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, cyano, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms, or a heteroaromatic group having 5 to 30 ring atoms, or combinations thereof.
5. A spiro organic compound according to claim 4, wherein: ar (Ar) 1 ，Ar 2 Independently selected from any one of the groups of the general formulas (C-1) to (C-9):
Figure FDA0003956352990000023
6. a spiro organic compound according to claim 1, characterized in that: the organic compound is selected from the following structures:
Figure FDA0003956352990000031
/>
Figure FDA0003956352990000041
/>
Figure FDA0003956352990000051
/>
Figure FDA0003956352990000061
/>
Figure FDA0003956352990000071
7. a mixture, characterized by: the mixture comprising at least one organic compound according to any one of claims 1 to 6 and at least one further organic functional material selected from the group consisting of hole injection materials, hole transport materials, electron injection materials, electron blocking materials, hole blocking materials, light emitting materials, host materials and organic dyes.
8. A composition characterized by: the composition comprises an organic compound according to any one of claims 1 to 6 or a mixture according to claim 7, and at least one organic solvent.
9. An organic electronic device comprising at least one functional layer, characterized in that: the functional layer comprises an organic compound according to any of claims 1 to 6 or a mixture according to claim 7 or is prepared from a composition according to claim 8.
10. The organic electronic device of claim 9, wherein: the organic electronic device is selected from an organic light emitting diode, an organic photovoltaic cell, an organic field effect transistor, an organic laser, an organic spin electronic device, an organic sensor and an organic plasmon emitting diode.
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