CN114075112A

CN114075112A - Fluorene compound and application thereof

Info

Publication number: CN114075112A
Application number: CN202010817966.XA
Authority: CN
Inventors: 何锐锋; 吴灿洁; 李冬云; 宋晶尧
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2020-08-14
Filing date: 2020-08-14
Publication date: 2022-02-22
Anticipated expiration: 2040-08-14
Also published as: CN114075112B

Abstract

The invention relates to a fluorene compound and application thereof, wherein the fluorene compound has a structure shown in a general formula (I):

wherein Ar is³～Ar⁴The same or different, each is independently selected from the group having the following structure:

Description

Fluorene compound and application thereof

Technical Field

The invention relates to the technical field of photoelectric materials, in particular to a fluorene compound and application thereof.

Background

The organic semiconductor material has diversity in synthesis, relatively low manufacturing cost and excellent optical and electrical properties, so that the organic semiconductor material is widely applied to the preparation of various photoelectric devices, such as flat panel displays, illumination and the like.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescence phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween, the organic layer having a multilayer 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 layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, 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, high responsiveness and the like.

In order to improve the light emitting efficiency of the organic electroluminescent device, various fluorescent and phosphorescent light emitting material systems have been developed, and most of the blue fluorescent materials have a too wide emission spectrum, poor color purity, and are not favorable for high-end display, and the synthesis of the fluorescent materials is complicated and is not favorable for large-scale mass production, and simultaneously, the OLED stability of the blue fluorescent materials needs to be further improved.

The luminescent layer of the blue organic electroluminescent element in the prior art adopts a host-guest doped structure. As the blue light guest compounds of the prior art, aryl vinyl amine compounds or pyrene compounds can be used. However, the device efficiency of the existing blue light material is still relatively low, the lifetime of the device is relatively short, and the full-color display performance is limited.

Disclosure of Invention

Based on this, there is a need for a fluorene compound that can improve the lifetime of the device and its application.

A fluorene compound has a structure shown in a general formula (I):

l is selected from: a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl or nonaromatic ring system having 5 to 40 ring atoms;

Ar¹-Ar²each independently selected from: a substituted or unsubstituted aryl group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaryl or nonaromatic ring system having 5 to 40 ring atoms;

Ar³-Ar⁴the same or different, each is independently selected from the group having the following structure:

wherein Ar is⁵、Ar⁶、Ar⁷Or Ar⁸Each independently selected from the group consisting of:

each occurrence of X is independently represented as CR¹Or N;

each occurrence of Y is independently selected from N (R)²)、C(R²R³) O or S;

R¹、R²、R³at each occurrence, is independently selected from: hydrogen, deuterium, a straight-chain alkyl group having 1 to 20C atoms, a deuterated straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a deuterated cyclic alkyl group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl group having 5 to 60 ring atoms, Substituted or unsubstituted heteroaryl having 5 to 60 ring atoms or combinations of these, adjacent R¹Form a ring or not form a ring;

a mixture comprising a fluorene compound as described above and at least one further organic functional material.

A composition comprising the fluorene compound and an organic solvent.

An organic electronic device comprising a functional layer comprising a fluorene compound or mixture as described above or prepared from a composition as described above.

The fluorene compound creatively connects two groups on 9, 9' -positions of fluorene by ethyl, and combines the selection of each substituent group, so that the rotation and the planarity of the groups are balanced, the light emitting and transmitting characteristics of the groups are favorably exerted, and the aims of improving the relevant performance (such as light emitting efficiency and service life) and stability of a light emitting device are fulfilled.

Detailed Description

In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, "optionally substituted" or "optionally further substituted with the following groups" means that the defined groups may or may not be substituted.

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 to be optionally substituted with art-acceptable groups including, but not limited to: c_1-30An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted by a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C_1-6An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms or a heteroaryl group having 5 to 10 ring atoms; said C is_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c_1-6Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms, halogen, hydroxy, nitro or amino.

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 atoms contained in the substituent are 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.

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. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-butylcyclohexyl, 2-butylheptyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-tert-butylhexyl, 2-butylhexyl, or a, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, 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 having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH)₃or-OMe), ethoxy (-O-CH)₂CH₃or-OEt) and tert-butoxy (-O-C (CH)₃)₃or-OtBu).

"aryl" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from the aromatic ring compound and may be a monocyclic aryl group, or a fused ring aryl group, or a polycyclic aryl group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl having 5 to 60 ring atoms" means an aryl group containing 5 to 60 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene, 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" means that on the basis of an aryl 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 60 ring atoms" refers to heteroaryl having 5 to 60 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, and quinazolinone.

In the present invention, m-membered aryl means aryl group containing m ring atoms, m-membered heteroaryl means heteroaryl group containing m ring atoms, for example: "5-10 membered aryl" refers to aryl groups containing 5-10 ring atoms, and "5-10 membered heteroaryl" refers to heteroaryl groups containing 5-10 ring atoms.

"amino" refers to a derivative of ammonia having the formula-N (X)₂Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amino groups include-NH₂-N (alkyl)₂NH (alkyl), -N (cycloalkyl)₂NH (cycloalkyl), -N (heterocyclyl)₂NH (heterocyclyl), -N (aryl)₂NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.

"halogen" or "halo" refers to F, Cl, Br, or I.

"alkylamino" refers to an amino group substituted with at least one alkyl group. Suitable examples include, but are not limited to: -NH₂、-NH(CH₃)、-N(CH₃)₂、-NH(CH₂CH₃)、-N(CH₂CH₃)₂。

"arylalkyl" refers to a hydrocarbyl radical derived from an alkyl radical having at least one hydrogen atom bonded to a carbon atom replaced by an aryl radical. Wherein the aryl moiety may include 5 to 20 carbon atoms and the alkyl moiety may include 1 to 9 carbon atoms. Suitable examples include, but are not limited to: benzyl, 2-phenyleth-1-yl, naphthylmethyl, 2-naphthyleth-1-yl, naphthobenzyl and 2-naphthophenyleth-1-yl.

In the present invention, "+" attached to a single bond denotes a connection site;

in the present invention, when the attachment site is not specified in the group, it means that a site optionally attachable to the group is used as the attachment site; for example: l is

The attachment site may be located at

Above, also can be located at

On a linked benzene ring, including but not limited to

In the present invention, when a fused site is not specified in a group, it means that an optionally fused site in the group is a fused site, and preferably two or more sites at the ortho position in the group are fused sites;

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

Wherein R is attached to any substitutable site of the pyridine ring, e.g. L is

Expression (a)

Any two of the V are attachment sites.

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

2R on the ring⁴May be the same as or different from each other.

In the present invention, "an optional number of hydrogens may be further substituted with deuterium" means that the corresponding substituent may or may not be deuterated.

As used herein, "deuterated" is conventionally understood in the art to mean that an optional number of H's on the target substituent are replaced with deuterium, for example: "deuterated alkyl having 1 to 20C atoms" means that an optional number of H in the alkyl group are substituted with deuterium.

Detailed explanation

The invention provides a fluorene compound which has a structure shown in a general formula (I):

each occurrence of X is independently represented as CR¹Or N; preferably, X is independently represented at each occurrence as CR¹；

Each occurrence of Y is independently selected from NR²、CR²R³O or S;

R¹、R²、R³at each occurrence, is independently selected from: hydrogen, deuterium, straight-chain alkyl having 1 to 20C atoms, deuterated straight-chain alkyl having 1 to 20C atoms, straight-chain alkyl having 1 to 20C atomsAlkoxy of a molecule, thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, deuterated branched alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, deuterated cyclic alkyl having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryl having 5 to 60 ring atoms or a combination of these groups, adjacent R¹Form a ring or not form a ring;

further, L is selected from: a substituted or unsubstituted condensed ring aryl group with 12-40 ring atoms, or a substituted or unsubstituted condensed ring heteroaryl group with 12-40 ring atoms;

further, L is selected from: a substituted or unsubstituted fused ring aryl group having 16 to 40 ring atoms, or a substituted or unsubstituted fused ring heteroaryl group having 16 to 40 ring atoms;

further, the aryl and heteroaryl groups are optionally further substituted with: hydrogen, deuterium, a straight-chain alkyl group having 1 to 20C atoms, a deuterated straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a deuterated cyclic alkyl group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl group having 5 to 60 ring atoms, Substituted or unsubstituted heteroaryl groups having 5 to 60 ring atoms or combinations of these groups.

Still further, the aryl and heteroaryl groups are optionally further substituted with: deuterium, straight-chain alkyl having 1 to 8C atoms, deuterated straight-chain alkyl having 1 to 8C atoms, alkoxy having 1 to 8C atoms, branched or cyclic alkyl having 3 to 8C atoms, deuterated branched or deuterated cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

R⁷selected from: deuterium, a straight-chain alkyl group having 1 to 8C atoms, a deuterated alkyl group having 1 to 8C atoms, an alkoxy group having 1 to 8C atoms, a deuterated alkoxy group having 1 to 8C atoms, a branched or cyclic alkyl group having 3 to 8C atoms, an aryl group having 5 to 10 ring atoms, or a heteroaryl group having 5 to 10 ring atoms.

Further, L is selected from the group having the following structure:

v is N or CR⁴(ii) a Preferably, V is selected from CR⁴；

W is NR⁵、CR⁵R⁶、SiR⁵R⁶、O、PR⁵、P(＝O)R⁵S, S ═ O or SO₂；

R⁴-R⁶Each occurrence is independently selected from: hydrogen, deuterium, straight-chain alkyl having 1 to 20C atoms, deuterated straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched-chain alkyl having 3 to 20C atoms, deuterated branched-chain alkyl having 3 to 20C atoms, cyclic alkyl having 3 to 20C atoms, deuterated cyclic alkyl having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, aminoFormyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, or a combination of these groups.

Further, L is selected from the group having the following structure:

wherein:

a and b are independently selected from any integer of 0-8;

c is selected from any integer of 0-12;

d is selected from any integer of 0-4;

e is selected from any integer of 0-2;

f is selected from any integer of 0-3;

m1 is selected from 0, 1 or 2; m2 is selected from 0, 1 or 2; .

Further, L is selected from the group having the following structure:

R⁴as defined above;

further, R⁴Each occurrence is independently selected from: hydrogen, deuterium, straight chain alkyl having 1 to 8C atoms, deuterated straight chain alkyl having 1 to 8C atoms, branched alkyl having 3 to 8C atoms, deuterated branched alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 8C atoms, deuterated cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

R⁵-R⁶each occurrence is independently selected from: utensil for cleaning buttockStraight chain alkyl having 1 to 8C atoms, deuterated straight chain alkyl having 1 to 8C atoms, branched alkyl having 3 to 8C atoms, deuterated branched alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 8C atoms, deuterated cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

R⁷selected from: deuterium, a straight chain alkyl group having 1 to 8C atoms, a branched alkyl group having 3 to 8C atoms, a cyclic alkyl group having 3 to 8C atoms, an aryl group having 5 to 10 ring atoms, or a heteroaryl group having 5 to 10 ring atoms.

Further, R⁴Each occurrence is independently selected from: hydrogen, deuterium, a straight chain alkyl group having 1 to 6C atoms, or a branched alkyl group having 1 to 6C atoms, a deuterated straight chain alkyl group having 1 to 6C atoms, or a deuterated branched alkyl group having 1 to 6C atoms;

further, R⁴Each occurrence is independently selected from: hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, or tert-pentyl, and an optional number of hydrogens in methyl, ethyl, isopropyl, tert-butyl, tert-pentyl may be substituted with deuterium; in one embodiment, all H atoms in methyl, ethyl, isopropyl, t-butyl, t-pentyl are deuterium substituted.

Further, R⁵-R⁶Each occurrence is independently selected from: straight chain alkyl having 1 to 6C atoms, branched chain alkyl having 1 to 6C atoms, deuterated straight chain alkyl having 1 to 6C atoms, deuterated branched chain alkyl having 1 to 6C atoms, aryl having 5 to 10 ring atoms, heteroaryl having 5 to 10 ring atoms, C_1-4Alkyl-substituted aryl having 5 to 10 ring atoms, or C_1-4Heteroaryl groups in which the alkyl group has 5 to 10 ring atoms;

further, R⁵-R⁶Each occurrence is independently selected from: methyl, ethyl, isopropyl, tert-butyl, tert-amyl, or phenyl, and methylAn optional number of hydrogens in the group, ethyl, isopropyl, t-butyl, t-pentyl or phenyl may be substituted with deuterium; in one embodiment, all H atoms in methyl, ethyl, isopropyl, t-butyl, t-pentyl are deuterium substituted.

Further, Ar¹-Ar²Each independently selected from the group consisting of:

wherein:

X₁at each occurrence, is independently selected from CR⁸Or N; preferably, X₁At each occurrence, is independently selected from CR⁸；

Y₁At each occurrence, is independently selected from N (R)⁹)、C(R⁹R¹⁰)、Si(R⁹R¹⁰)、O、C＝N(R⁹)、C＝C(R⁹R¹⁰)、P(R⁹)、P(＝O)R⁹S, S ═ O or SO₂；

R⁸-R¹⁰At each occurrence, is independently selected from: hydrogen, deuterium, a straight-chain alkyl group having 1 to 20C atoms, a deuterated straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a deuterated cyclic alkyl group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl group having 5 to 60 ring atoms, Substituted or unsubstituted heteroaryl groups having 5 to 60 ring atoms or combinations of these groups.

Further, R⁸-R¹⁰At each occurrence, is independently selected from: hydrogenDeuterium, straight-chain alkyl having 1 to 8C atoms, branched or cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

R⁷selected from: deuterium, alkyl having 1 to 8C atoms, branched alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 20C atoms, aryl having 5 to 10 ring atoms, or heteroaryl having 5 to 10 ring atoms.

Further, R⁸-R¹⁰At each occurrence, is independently selected from: hydrogen, deuterium, straight-chain alkyl having 1 to 8C atoms, branched-chain alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 20C atoms, aryl having 5 to 10 ring atoms, heteroaryl having 5 to 10 ring atoms, C_1-6Alkyl-substituted aryl having 5 to 10 ring atoms, or C_1-6Alkyl-substituted heteroaryl having 5 to 10 ring atoms;

further, R⁸-R¹⁰At each occurrence, is independently selected from: H. methyl, ethyl, isopropyl, tert-butyl, tert-amyl, or phenyl, and an optional number of hydrogens in the methyl, ethyl, isopropyl, tert-butyl, tert-amyl, or phenyl may be substituted with deuterium;

in one embodiment, Ar¹-Ar²Each independently selected from the group consisting of:

in one embodiment, Ar¹-Ar²Selected from the following structures:

in one embodiment, R⁸When present multiple times, at least one R⁸Selected from straight chains of 1 to 20C atomsAlkyl, branched with 3 to 20C atoms or cyclic alkyl with 3 to 20C atoms.

Further, Ar¹-Ar²Each independently selected from the group consisting of:

in one embodiment, Ar⁵、Ar⁶、Ar⁷Or Ar⁸Each independently selected from the group consisting of:

further, the structure shown in the general formula (I) at least comprises an alkyl;

further, the fluorene compound has a structure represented by any one of the following general formulas (I-1) to (I-5):

in one embodiment, L and Ar¹-Ar²At least one of which has a linear alkyl group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, a deuterated linear alkyl group having 1 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, or a deuterated cyclic alkyl group having 3 to 20C atoms.

In one embodiment, L contains a straight chain alkyl group of 1 to 20C atoms, a branched alkyl group of 3 to 20C atoms, or a cyclic alkyl group of 3 to 20C atoms. Further, at least one R⁴Selected from a straight chain alkyl group of 1 to 20C atoms, a branched alkyl group of 3 to 20C atoms or a cyclic alkyl group of 3 to 20C atoms.

In one embodiment, Ar¹-Ar²At least one of which has a straight-chain alkyl group of 1 to 20C atoms, a branched chain of 3 to 20C atoms, orCyclic alkyl groups having 3 to 20C atoms. Preferably, Ar¹-Ar²A straight-chain alkyl group, a branched-chain alkyl group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, each containing 1 to 20C atoms.

Further, the fluorene compound is selected from the following compounds:

further, the fluorene compound is a compound having a light-emitting property, and light emission refers to photoluminescence or electroluminescence.

Further, the luminescence wavelength of the fluorene compound is between 300-1000 nm. Further, the luminescence wavelength of the fluorene compound is between 350-900 nm. Furthermore, the luminescence wavelength of the fluorene compound is between 400 and 800 nm. In one embodiment, the luminescent wavelength of the fluorene compound is between 400 and 600 nm. Further, the luminescence wavelength of the fluorene compound is between 400-500 nm.

Further, the fluorene compound is a guest material; further, the fluorene compound is a blue guest material.

The invention also relates to application of the fluorene compound in preparation of organic electronic devices.

The invention further relates to a mixture comprising at least one fluorene compound as described above, and at least one other organic functional material 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 WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In one embodiment, the further organic functional material is selected from host materials, which are used as co-hosts in electronic devices.

The invention also relates to a composition comprising at least one fluorene compound or a mixture thereof 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.

The invention also provides a composition which comprises the fluorene compound and a solvent. Further, the solvent is selected 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, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;

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-trimethoxybenzene, 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, methyl 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, fenchylone, 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 invention is characterized by comprising at least one organic compound or polymer 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, 1,1, 1-trichloroethane, 1,1,2, 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:

delta d (dispersion force) is within the range of 17.0-23.2 MPa1/2, especially within the range of 18.5-21.0 MPa 1/2;

δ p (polar force) is in the range of 0.2-12.5 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2;

delta h (hydrogen bonding force) is in the range of 0.9-14.2 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2.

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 contain 0.01 to 10 wt%, preferably 0.1 to 15 wt%, more preferably 0.2 to 5 wt%, and most preferably 0.25 to 3 wt% of the 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 the production of organic electronic devices, particularly preferably by a printing or coating production process.

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, enhancing adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the fluorene-based compound, the mixture or the composition as described above in an Organic electronic device, which can 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 (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferably OLEDs. In the embodiment of the present invention, the aromatic amine compound is preferably used for a hole transport layer of an OLED device.

The invention also provides a functional layer which comprises the fluorene compound; further, the functional layer is a light emitting layer, the light emitting layer includes a host material and a guest material, and the guest material is the fluorene compound.

The invention further relates to an organic electronic device comprising at least one functional layer comprising a fluorene compound, a mixture or a composition as described above. Further, the organic electronic device comprises a cathode, an anode and at least one functional layer, wherein the functional layer comprises one aromatic amine compound or a mixture thereof or is prepared from the composition. The functional layer is 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); preferably, the functional layer is selected from a light emitting layer.

The Organic electronic device can 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 (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. 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, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. 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 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. 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 0.2 eV. 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 anode materials are known and 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), and the like. In certain embodiments, the anode is pattern structured.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. 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 of 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 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. 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), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1200nm, preferably 350 to 1000nm, and more preferably 400 to 900 nm.

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 below with reference to specific examples.

EXAMPLE 1 Synthesis of Compound M1

Synthesis of intermediate M1-4: adding M1-2(31.2g, 100mmol) into a 500ml three-necked flask, adding 200ml anhydrous tetrahydrofuran, stirring for dissolving, replacing nitrogen for three times, cooling the reaction liquid to-78 ℃ under the protection of nitrogen, stirring for half an hour, slowly dropwise adding 45ml butyl lithium solution, controlling the temperature to be-80-60 ℃ for reacting for 1h, and then dropwise adding M1-1(20.8g, 100mmol) tetrahydrofuran solution in the temperature range. After the addition, slowly raising the temperature to room temperature for further reaction for 2 hours, adding a saturated solution of ammonium chloride to quench the reaction, adding water for dilution, separating liquid, extracting an aqueous phase with DCM, combining organic phases, concentrating to remove a solvent to obtain M1-3 yellow oily matter, then adding 100ml of acetic acid and 20ml of concentrated hydrochloric acid, and heating to 60 ℃ for reaction overnight. Cooling, concentrating to remove solvent, dichloromethane and water solution, mixing organic phases, washing with saturated sodium bicarbonate to neutrality, washing with saturated sodium chloride water, drying with anhydrous sodium sulfate, purifying and decolorizing with column chromatography to obtain white solid with yield of 51%

Synthesis of intermediate M1-6: under a nitrogen atmosphere, compound M1-4 (25.3g,60mmol), (6.42g, 60mmol) compound M1-5, (5.73g, 30mmol) cuprous iodide, (3.42g, 30mmol) trans-cyclohexanediamine, (19.1g, 60mmol) potassium phosphate and 150mL toluene were added to a 300mL three-necked flask, heated and stirred to 110 ℃ for 12 hours, the reaction was terminated, cooled to room temperature, the filtrate was suction filtered, most of the solvent was rotary evaporated, the solvent was washed with dichloromethane-dissolved water 3 times, and the organic solution was collected and purified by column chromatography on silica gel with a yield of 70%.

Synthesis of compound M1: under nitrogen atmosphere, adding (27.0g, 60mmol) compound M1-6, (13.3g, 30mmol) compound M1-7, (5.73g, 30mmol) cuprous iodide, (3.42g, 30mmol) trans-cyclohexanediamine, (19.1g, 60mmol) potassium phosphate and 150mL toluene into a 300mL three-neck flask, heating and stirring to 110 ℃ for reaction for 12 hours, finishing the reaction, cooling to room temperature, filtering the filtrate, rotary evaporating most of the solvent, washing with dichloromethane dissolved water for 3 times, collecting organic solution, mixing with silica gel, and purifying by passing through a column with yield of 60%

Example 2 Synthesis of Compound M2

Synthesis of intermediate M2-4: according to the synthesis of compound M1-4, compound M2-2 (15.9g,60mmol) was substituted for compound M1-2;

synthesis of intermediate M2-6: according to the synthesis of compound M1-6, compound M2-4 (22.68g,60mmol) and compound M2-5 (14.34g,60mmol) were substituted for compound M1-4 and M1-5;

synthesis of compound M2: according to the synthesis of compound M1, compound M2-6 (34.8g,60mmol) and compound M2-7 (10.8g,30mmol) were substituted for compound M1-6 and M1-7.

Example 3: synthesis of Compound M3

Synthesis of intermediate M3-4: according to the synthesis method of the compound M1-4;

synthesis of intermediate M3-6: according to the synthesis method of compound M1-6, compound M3-5 (8.1g,60mmol) was substituted for compound M1-5;

synthesis of compound M3: according to the synthesis of compound M1, compound M3-6 (29.6g,60mmol) and compound M3-7 (10.8g,30mmol) were substituted for compound M1-6 and M1-7.

Example 4 Synthesis of Compound M4

Synthesis of intermediate M4-4: according to the synthesis method of the compound M1-4;

synthesis of intermediate M4-6: according to the synthesis method of compound M1-6, compound M4-5 (9.4g,60mmol) was substituted for compound M1-5;

synthesis of compound M4: according to the synthesis of compound M1, compound M4-6 (30.0g,60mmol) and compound M4-7 (10.0g,30mmol) were substituted for compound M1-6 and M1-7.

EXAMPLE 5 Synthesis of Compound M5

Synthesis of intermediate M5-4: according to the synthesis method of the compound M1-4;

synthesis of intermediate M5-6: according to the synthesis method of compound M1-6, compound M5-5 (11.0g,60mmol) was substituted for compound M1-5;

synthesis of intermediate M5-9: according to the synthesis method of compound M1-4, compound M5-7 (20.0g,60mmol) was substituted for compound M1-2;

synthesis of intermediate M5-11 according to the method for the synthesis of Compound M1-6, Compound M5-9 (25.6g,60mmol) and Compound M5-10 (7.3g,60mmol) are substituted for Compound M1-4 and M1-5;

synthesis of intermediate M5-13 according to the method for the synthesis of Compound M1-6, Compound M5-6 (30.8g,60mmol) and Compound M5-12 (23.2g,60mmol) were substituted for Compound M1-4 and M1-5.

Synthesis of Compound M5 according to the method for synthesizing Compound M5-13, Compound M5-11 (30.8g,60mmol) and Compound M5-13 (49.0g,60mmol) were substituted for Compound M5-6 and M5-12.

Example 6 Synthesis of Compound M6

Synthesis of intermediate M6-4: according to the synthesis method of the compound M1-4;

synthesis of intermediate M6-6: according to the synthesis of compound M1-6, compound M6-5 (12.5g,60mmol) was substituted for compound M1-5;

synthesis of compound M6: according to the synthesis of compound M1, compound M6-6 (33.0g,60mmol) and compound M6-7 (15.5g,30mmol) were substituted for compound M1-6 and M1-7.

Example 7 Synthesis of Compound M7

Synthesis of intermediate M7-4: according to the synthesis of compound M2-4, compound M7-1 (15.5g,60mmol) and compound M7-2 (16.1g,60mmol) were substituted for compound M2-1 and M2-2;

synthesis of intermediate M7-6: according to the synthesis of compound M2-6, compound M7-4 (25.68g,60mmol) and compound M7-5 (7.26g,60mmol) were substituted for compound M2-4 and M2-5

Synthesis of compound M7: according to the synthesis of compound M2, compound M7-6 (30.8g,60mmol) and compound M7-7 (17.3g,30mmol) were substituted for compound M2-6 and M2-7.

Example 8 Synthesis of Compound M8

Synthesis of intermediate M8-4: according to the synthesis of compound M7-4, compound M8-1 (12.5g,60mmol) was substituted for compound M7-1;

synthesis of intermediate M8-6: according to the synthesis of compound M7-6, compound M8-4 and the alternative compound M7-4 (22.7g,60 mmol);

synthesis of compound M8: according to the synthesis of compound M7, compound M8-6 (27.8g,60mmol) and compound M8-7 (20.7g,30mmol) were substituted for compound M7-6 and M7-7.

Example 9 Synthesis of Compound M9

Synthesis of intermediate M9-4: according to the synthesis of compound M8-4, compound M9-1 (17.2g,60mmol) and compound M9-2 (14.0g,60mmol) were substituted for compound M8-1 and M8-2;

synthesis of intermediate M9-6: according to the synthesis of compound M8-6, compound M9-4 (25.3g,60mmol) and compound M9-5 (9.4g,60mmol) were substituted for compound M8-4 and M8-5.

Synthesis of compound M9: according to the synthesis of compound M8, compound M9-6 (30g,60mmol) was substituted for compound M8-6

Example 10 Synthesis of Compound M10

Synthesis of intermediate M10-4: according to the synthesis of compound M9-4, compound M10-1 (17.2g,60mmol) was substituted for compound M9-1;

synthesis of intermediate M10-6: according to the synthesis of compound M9-6, compound M10-4 (25.3g,60mmol) and compound M10-5 (10.1g,60mmol) were substituted for compound M9-4 and M9-5;

synthesis of compound M10: according to the synthesis of compound M9, compound M10-6 (30.1g,60mmol) and compound M10-7 (15g,30mmol) were substituted for compound M9-6 and M9-7;

example 11 Synthesis of Compound M11

Synthesis of intermediate M11-4: according to the synthesis method of compound M8-4, compound M11-1 (12.48g,60mmol) was substituted for compound M8-1;

synthesis of intermediate M11-6: according to the synthesis of compound M8-6, compound M11-4 (31.74g,60mmol) and compound M11-5 (7.26g,60mmol) were substituted for compound M8-4 and M8-5;

synthesis of compound M11: according to the synthesis of compound M8, compound M11-6 (33.18g,60mmol) and compound M11-7 (10.18g,30mmol) were substituted for compound M8-6 and M8-7;

comparative example 1

Among them, Ref-1 is described in patent CN 108129332A.

Preparation and characterization of OLED device

Materials used for the layers of the OLED device:

HIL: a triarylamine derivative (HIM);

HTL: a triarylamine derivative (HTM);

host is anthracene derivative;

the volume of the Dopan: compound M1-compound M10, Ref-1.

Having an ITO/HIL (40nm)/HTL (100 nm)/Host: the preparation steps of the OLED device with 5% of Dopan (50nm)/ETL (25nm)/LiQ (1nm)/Al (150 nm)/cathode are as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. sequentially forming a film by using a solution processing method on HIL (40nm), HTL (100nm) and EML (50 nm);

c. ETL (25 nm): under high vacuum (1X 10)^-6Mbar, mbar) by thermal evaporation;

d. cathode LiQ/Al (1nm/150nm) in high vacuum (1X 10)^-6Millibar) hot evaporation;

e. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

The current-voltage (J-V) characteristics of the organic light emitting diodes of blue device examples M1 to M10 and comparative example 1 were tested using a characterization apparatus while recording important parameters such as efficiency, lifetime (see table 1) and external quantum efficiency. In table 1, all external quantum efficiencies and lifetimes are relative values with respect to the organic light emitting diode of comparative example 1.

TABLE 1

OLED device	Guest material	EQE	T90@1000nits
				Example 1	M1	1.74	1.85
Example 2	M2	1.65	1.76
				Example 3	M3	1.52	1.63
Example 4	M4	1.46	1.54
				Example 5	M5	1.34	1.45
Example 6	M6	1.57	1.68
				Example 7	M7	1.86	1.95
Example 8	M8	2.25	2.32
				Example 9	M9	2.06	2.17
Example 10	M10	1.94	2.06
				Example 11	M11	1.69	1.81
Comparative example 1	Ref-1	1	1

It can be seen that the efficiency and lifetime of the electrical devices comprising the compounds of the above examples are improved to some extent, especially the luminous efficiency and lifetime of the light-emitting devices comprising the guest material M9 of example 9. It shows that the blue light device prepared based on the compound of the invention has greatly improved efficiency and service life.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

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

1. A fluorene compound having a structure represented by general formula (I):

each occurrence of X is independently represented as CR¹Or N;

each occurrence of Y is independently selected from NR²、CR²R³O or S;

R¹、R²、R³at each occurrence, is independently selected from: hydrogen, deuterium, straight-chain alkyl having 1 to 20C atoms, deuterated straight-chain alkyl having 1 to 20C atoms, alkoxy having 1 to 20C atoms, thioalkoxy having 1 to 20C atoms, branched-chain alkyl having 3 to 20C atoms, deuterated branched-chain alkyl having 3 to 20C atomsAlkanyl, cyclic alkyl having 3 to 20C atoms, deuterated cyclic alkyl having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl having 5 to 60 ring atoms, a substituted or unsubstituted heteroaryl having 5 to 60 ring atoms, or a combination of these groups, adjacent R¹With or without rings formed from each other.

2. The fluorene-based compound according to claim 1, wherein L is selected from the group having the following structure:

v is N or CR⁴；

R⁴-R⁶Each occurrence is independently selected from: hydrogen, deuterium, a straight-chain alkyl group having 1 to 20C atoms, a deuterated straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a deuterated cyclic alkyl group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted group having 5 to 60 ring atomsSubstituted or unsubstituted heteroaryl having 5 to 60 ring atoms, or a combination of these groups.

3. The fluorene-based compound according to claim 2, wherein L is selected from the group having the following structure:

R⁴each occurrence is independently selected from: hydrogen, deuterium, straight chain alkyl having 1 to 8C atoms, deuterated straight chain alkyl having 1 to 8C atoms, branched alkyl having 3 to 8C atoms, deuterated branched alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 8C atoms, deuterated cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

R⁵-R⁶each occurrence is independently selected from: straight chain alkyl having 1 to 8C atoms, deuterated straight chain alkyl having 1 to 8C atoms, branched alkyl having 3 to 8C atoms, deuterated branched alkyl having 3 to 8C atoms, cyclic alkyl having 3 to 8C atoms, deuterated cyclic alkyl having 3 to 8C atoms, aryl having 5 to 20 ring atoms, heteroaryl having 5 to 20 ring atoms, R⁷Substituted aryl having 5 to 20 ring atoms, R⁷Substituted heteroaryl having 5 to 20 ring atoms;

4. The fluorene-based compound according to claim 1, wherein Ar is Ar¹-Ar²Each independently selected fromThe following groups:

wherein:

X₁at each occurrence, is independently selected from CR⁸Or N;

Y₁at each occurrence, independently selected from NR⁹、CR⁹R¹⁰、SiR⁹R¹⁰、O、C＝N(R⁹)、C＝C(R⁹R¹⁰)、P(R⁹)、P(＝O)R⁹S, S ═ O or SO₂；

R⁸-R¹⁰At each occurrence, is independently selected from: hydrogen, deuterium, a straight-chain alkyl group having 1 to 20C atoms, a deuterated straight-chain alkyl group having 1 to 20C atoms, an alkoxy group having 1 to 20C atoms, a thioalkoxy group having 1 to 20C atoms, a branched alkyl group having 3 to 20C atoms, a deuterated branched alkyl group having 3 to 20C atoms, a cyclic alkyl group having 3 to 20C atoms, a deuterated cyclic alkyl group having 3 to 20C atoms, a silyl group, a ketone group having 1 to 20C atoms, an alkoxycarbonyl group having 2 to 20C atoms, an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl group, a haloformyl group, a formyl group, an isocyano group, an isocyanate, a thiocyanate, an isothiocyanate, a hydroxyl group, a nitro group, CF3, Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aryl group having 5 to 60 ring atoms, Substituted or unsubstituted heteroaryl groups having 5 to 60 ring atoms, or combinations of these groups.

5. The fluorene-based compound according to claim 4, wherein Ar is Ar¹-Ar²Each independently selected from the group consisting of:

6. the fluorene-based compound according to claim 5, wherein R is⁸When present multiple times, at least one R⁸Selected from a straight chain alkyl group of 1 to 20C atoms, a branched alkyl group of 3 to 20C atoms or a cyclic alkyl group of 3 to 20C atoms.

7. The fluorene compound according to any one of claims 1 to 6, which has a structure represented by any one of the following general formulae (I-1) to (I-5):

8. the fluorene-based compound according to claim 1, which is selected from the following compounds:

9. a mixture comprising the fluorene compound according to any one of claims 1 to 8 and at least one other organic functional material.

10. A composition comprising the fluorene compound according to any one of claims 1 to 8 and an organic solvent.

11. An organic electronic device comprising a functional layer, wherein the functional layer comprises the fluorene-based compound of any one of claims 1-8 or the mixture of claim 9 or prepared from the composition of claim 10.

12. The organic electronic device according to claim 11, wherein the functional layer is a light emitting layer.