CN117466921A - Boron-containing organic compounds, mixtures, compositions and organic electronic devices - Google Patents

Boron-containing organic compounds, mixtures, compositions and organic electronic devices Download PDF

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Publication number
CN117466921A
CN117466921A CN202310128781.1A CN202310128781A CN117466921A CN 117466921 A CN117466921 A CN 117466921A CN 202310128781 A CN202310128781 A CN 202310128781A CN 117466921 A CN117466921 A CN 117466921A
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atoms
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boron
organic compound
substituted
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宋鑫龙
雷金龙
何锐锋
宋晶尧
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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Abstract

The application disclosesA boron-containing organic compound, a mixture, a composition and an organic electronic device are provided, wherein the boron-containing organic compound has a structure shown as a general formula (1-1) or a general formula (1-2), is used in an organic electronic device, particularly used as a luminescent material in a luminescent layer of the organic electronic device, and can improve the luminous efficiency and service life of the organic electronic device.

Description

Boron-containing organic compounds, mixtures, compositions and organic electronic devices
Technical Field
The application relates to the technical field of luminescent materials, in particular to a boron-containing organic compound, a mixture, a composition and an organic electronic device.
Background
Organic semiconductor materials are synthesized in a variety of ways, are relatively inexpensive to manufacture, and have excellent optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have advantages of wide viewing angle, fast reaction time, low operating voltage, thin panel thickness, etc. in applications of optoelectronic devices such as flat panel displays and illumination, and thus have a wide development potential.
In order to improve the luminous efficiency of the organic light emitting diode, various luminescent material systems based on fluorescence and phosphorescence have been developed. Among them, the organic light emitting diode using the fluorescent material has a characteristic of high reliability, but its internal electroluminescent quantum efficiency is limited to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3. Organic light emitting diodes using phosphorescent materials have achieved almost 100% internal electroluminescent quantum efficiency, but phosphorescent OLEDs also produce the Roll-off effect, i.e., the luminous efficiency decreases rapidly with increasing current or brightness, which is particularly disadvantageous for high brightness applications.
To date, conventional phosphorescent materials having practical use values are iridium-and platinum-containing metal complexes, however, such raw materials are rare and expensive, and the synthesis of the metal complexes is complicated, resulting in high costs. In order to overcome the above problems, adachi proposes the concept of reverse internal conversion, i.e., the use of organic compounds instead of metal complexes as light emitting materials, which can achieve high efficiency comparable to phosphorescent OLEDs. This concept has been achieved by various combinations of materials, such as composite excited state materials, thermally-excited delayed fluorescence (TADF) materials, and the like.
However, the performance of conventional TADF materials, both in terms of efficiency and lifetime, is still somewhat different from that of phosphorescent materials.
Disclosure of Invention
In view of this, the present application provides a boron-containing organic compound as a novel class of light-emitting materials, which is used in organic electronic devices, aiming at improving the problems of low light-emitting efficiency and short lifetime of organic electronic devices.
The technical scheme of the application is as follows:
a boron-containing organic compound having a structure represented by the general formula (1-1) or the general formula (1-2):
wherein:
X 1 、X 3 、X 5 、X 6 each independently selected from NR 1 、O，X 2 、X 4 Each independently selected from NR 1 O, S, se or none;
Ar 1 -Ar 9 each independently selected from a substituted or unsubstituted aromatic group having 6 to 30C atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;
a is selected from single bond, NR 1 、O、S；
R 1 Each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, or cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atomsAn alkylene radical having 1 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, thiocyanate, isothiocyanate, hydroxy, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 30 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 30 ring atoms substituted or unsubstituted, or a combination of these groups.
When a defined group is substituted, the defined group may be substituted with one or more substituents independently selected from the group consisting of: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl.
Correspondingly, the application also provides a mixture which comprises the boron-containing organic compound and at least one organic functional material, wherein the organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material, a light-emitting host material or an organic dye.
Accordingly, the present application also provides a composition comprising the above boron-containing organic compound or the above mixture, and at least one organic solvent.
Correspondingly, the application also provides an organic electronic device, which comprises at least one organic functional layer, wherein the organic functional layer comprises the boron-containing organic compound or the mixture, or the organic functional layer is prepared from the composition.
Compared with the prior art, the boron-containing organic compound has the following beneficial effects:
the whole molecular structure of the boron-containing organic compound has better conjugation and planarity, so that the rigidity and stability of the organic compound molecule are improved; meanwhile, the molecular structure can increase the number of solubilizing groups, so that the solubility of the organic compound molecules is improved, the organic compound is easier to purify, the purity of the organic compound is improved, and the purposes of improving the luminous efficiency of the device and prolonging the service life of the device are achieved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of an organic electronic device according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, based on the embodiments herein, which are obtained by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and explanation only and is not intended to limit the present application. In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used to generally refer to the upper and lower directions of the device in actual use or operation, and in particular, the directions of the drawings in the drawings. In addition, in the description of the present application, the term "comprising" means "including but not limited to," the term "plurality" means "two or more," and the term "and/or" includes any and all combinations of one or more of the associated listed items. Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a 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 range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
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 herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In this application, the composition and the printing ink, or ink, have the same meaning and are interchangeable.
In this application, aromatic groups, aromatic ring systems have the same meaning and are interchangeable.
In this application, heteroaromatic groups, heteroaromatic ring systems have the same meaning and are interchangeable.
In the present application, "substituted" means that a hydrogen atom in a substituted group is substituted with a substituent.
In the present invention, the same substituent may be independently selected from different groups when it appears multiple times. 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, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, -NR' R ", silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and which may be further substituted with substituents acceptable in the art; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to: H. deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atoms, cyano groups, isocyano groups, nitro groups or halogen groups, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 10 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, trifluoromethyl groups, and which may be further substituted with substituents acceptable in the art.
In the present invention, the "number of ring atoms" means 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, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, 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.
"aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removal of one hydrogen atom, which 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 a polycyclic species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group having 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, fluoranthryl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenyl, acenaphthylenyl 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 acenaphthene, fluorene, or 9, 9-diaryl fluorene, triarylamine, diaryl ether systems in particular should also be included in the definition of aryl groups.
"heteroaryl or heteroaromatic group" means that at least one carbon atom is replaced by a non-carbon atom on the basis of an aryl group, which may be an N atom, an O atom, an S atom, or the like. 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 the heteroaryl is optionally further substituted, suitable examples include, but are not limited to: thienyl, furyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiophenoyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, primary pyridyl, quinazolinonyl, dibenzothienyl, dibenzofuranyl, carbazolyl, and derivatives thereof.
In the present inventionIn this, the "alkyl" may represent 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 this term, e.g., "C 1-9 Alkyl "means an alkyl group containing 1 to 9 carbon atoms, and each occurrence may be, independently of the other, C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl, C 6 Alkyl, C 7 Alkyl, C 8 Alkyl or C 9 An alkyl group. 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 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.
In the present application, the abbreviations of the substituents correspond to: n-n, sec-sec, i-iso, t-tert, o-o, m-m, p-pair, memethyl, et ethyl, pr propyl, bu butyl, am-n-pentyl, hx hexyl, cy cyclohexyl.
In the present invention, the silyl group may be represented by the formula-Si (Y101) (Y102) (Y103), and each of Y101, Y102, and Y103 may be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Examples of the silyl group include trialkylsilyl groups and triarylsilyl groups, and specific examples thereof include trimethylsilyl groups, triethylsilyl groups, t-butyldimethylsilyl groups, vinyldimethylsilyl groups, propyldimethylsilyl groups, triphenylsilyl groups, diphenylsilyl groups, phenylsilyl groups, and the like, but examples are not limited thereto.
"amine group" refers to a derivative of an amine having the formula-N (X) 2 Wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, or the like. Non-limiting types of amine groups include-NH 2 -N (alkyl) 2 -NH (alkyl), -N (cycloalkyl) 2 -NH (cycloalkyl), -N (heterocyclyl) 2 -NH (heterocyclyl), -N (aryl) 2 -NH (aryl), -N (alkyl) (heterocyclyl), -N (cycloalkyl) (heterocyclyl), -N (aryl) (heteroaryl), -N (alkyl) (heteroaryl), and the like.
In the present invention, as defined herein, hydroxyl means-OH, carboxyl means-COOH, carbonyl means-C (=o) -, amino means-NH 2, formyl means-C (=o) H, haloformyl means-C (=o) Z (wherein Z represents halogen), carbamoyl means-C (=o) NH2, isocyanato means-NCO, isothiocyanato means-NCS.
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 containing 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 t-butoxy (-O-C (CH) 3 ) 3 or-OtBu).
In the present invention "×" associated with a single bond represents a linking or fusing site;
in the present invention, when no linking site is specified in the group, an optionally-ligatable site in the group is represented as a linking site;
in the present invention, when no condensed site is specified in the group, it means that an optionally condensed site in the group is used as a condensed site, and preferably two or more sites in the group at ortho positions are condensed sites;
In the present invention, when the same group contains a plurality of substituents of the same symbol, each substituent may be the same or different from each other, for exampleThe 6R groups on the benzene ring may be the same or different from each other.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR in (2) is attached to any substitutable site of the benzene ring, e.g.>Representation->Can be combined with->Optionally substituted positions on the substrate form a fused ring.
In the present invention, "adjacent group" means that there is no substitutable site between two substituents.
In the present invention, "adjacent two R's are mutually cyclic" means a ring system formed by connecting two adjacent R's to each other, and the ring system may be selected from aliphatic hydrocarbon rings, aliphatic heterocyclic rings, aromatic hydrocarbon rings or aromatic heterocyclic rings. Preferably, a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 10 ring atoms may be formed; more preferably, a substituted or unsubstituted ring having 6 atoms is formedAn aromatic or heteroaromatic group. Preferably, can be formed into
As used in the present invention, "a combination thereof", "any combination thereof", "combination", and the like include all suitable combinations of any two or more of the listed items.
In the present invention, "further", "still further", "particularly" and the like are used for descriptive purposes to indicate differences in content but should not be construed as limiting the scope of the invention.
In the present invention, "optional" means optional or not, that is, means any one selected from two parallel schemes of "with" or "without". If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
A boron-containing organic compound having a structure represented by the general formula (1-1) or the general formula (1-2):
wherein:
X 1 、X 3 、X 5 、X 6 each independently selected from NR 1 、O，X 2 、X 4 Each independently selected from NR 1 O, S, se or none;
Ar 1 -Ar 9 each independently selected from a substituted or unsubstituted aromatic group having 6 to 30C atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;
a is selected from single bond, NR 1 、O、S；
R 1 Each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched alkyl having 3 to 20C atoms, or cyclic alkyl having 3 to 20C atoms, branched alkoxy having 3 to 20C atoms, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, alkenyl having 1 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 30 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 30 ring atoms substituted or unsubstituted, or a combination of these groups;
when a defined group is substituted, the defined group may be substituted with one or more substituents independently selected from the group consisting of: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl.
In some embodiments, the boron-containing organic compound is selected from any one of the structures represented by the general formulae (2-1) to (2-3):
in some embodiments, ar 1 -Ar 2 、Ar 5 -Ar 9 Each occurrence is independently selected from one or a combination of several structures represented by formulas (B-1) to (B-7):
Wherein:
x is independently selected from CR for each occurrence 2 ；
Y is independently selected from NR at each occurrence 3 S or O;
R 2 、R 3 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy 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, hydroxyl, nitro, amino, -CF 3 -Cl, -Br, -F, a substituted or unsubstituted aromatic group having 6 to 20C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups;
When a defined group is substituted, the defined group may be substituted with one or more substituents independently selected from the group consisting of: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl.
In some embodiments, the boron-containing organic compound is selected from any one of the structures represented by the general formulae (3-1) to (3-6):
wherein R represents a substituent.
In some embodiments, the structure of the boron-containing organic compound is selected from any of the structures represented by the general formulas (4-1) to (4-7):
wherein Z is independently selected from NR for each occurrence 1 O or S.
In some embodiments, X 1 、X 3 、X 5 、X 6 Each independently selected from NR 4 、O，X 2 、X 4 Each independently selected from NR 4 O, S, se or none;
R 4 、Ar 8 and Ar is a group 9 Each independently selected from the following structures:
x is independently selected from CR for each occurrence 5 ；
R 5 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an aromatic group having 6 to 20C atoms, or a combination of these groups.
In some embodiments, R 4 、Ar 8 And Ar is a group 9 Each independently selected from the following structures:
as an example, in some embodiments, the boron-containing organic compounds of the present application may be selected from, but are not limited to, any of the following structures:
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it is understood that H in the structural formula of the above organic compound may be further substituted.
In some embodiments, the boron-containing organic compounds of the present application may be applied as organic functional materials in functional layers of organic electronic devices, in particular in functional layers of OLED devices. The organic functional material may be, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting guest material (Emitter), a light emitting Host material (Host Emitter), and an organic dye.
In some embodiments, the boron-containing organic compounds described herein are used in light emitting layers. In at least one embodiment, the boron-containing organic compounds described herein are used in the light-emitting layer as light-emitting layer guest materials.
In some embodiments, the boron-containing organic compounds described herein are used in the light-emitting layer as blue light-emitting materials.
The present application further relates to a mixture comprising at least one boron-containing organic compound as described above and at least one further organic functional material. The another organic functional material is selected from the group consisting of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting guest material (Emitter), a light emitting host material, and an organic dye. Wherein the luminophore is selected from singlet luminophores (fluorescent luminophores), triplet luminophores (phosphorescent luminophores) and organic thermally excited delayed fluorescence materials (TADF materials). Details of various organic functional materials are found in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.
In one embodiment, the another organic functional material is selected from the group consisting of host materials; further, the another organic functional material is selected from blue host materials.
The present application also relates to a composition comprising at least one boron-containing organic compound or mixture as described above, and at least one organic solvent.
It will be appreciated that the composition may also be referred to as an ink.
When used in the printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a particular substrate and a particular printing method. In some embodiments, an ink according to the present application has a surface tension in the range of 19dyne/cm to 50dyne/cm at an operating temperature or at 25 ℃; more preferably 22dyne/cm to 35dyne/cm; preferably from 25dyne/cm to 33dyne/cm. In some embodiments, inks according to the present application have a viscosity in the range of 1cps to 100cps at the operating temperature or 25 ℃; preferably 1cps to 50cps; more preferably 1.5cps to 20cps; and preferably from 4.0cps to 20cps. The inks so formulated will facilitate inkjet printing.
The organic solvent is at least one selected from aromatic or heteroaromatic based solvents, ester based solvents, aromatic ketone based solvents, aromatic ether based solvents, aliphatic ketones, aliphatic ethers, alicyclic compounds, olefin compounds, boric acid ester compounds and phosphoric acid ester compounds.
In at least one embodiment, the organic solvent is selected from aromatic or heteroaromatic based solvents in the composition.
The aromatic or heteroaromatic based solvent may be selected from, but is not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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-phenylpropylpyridine, 1, 3-dimethylquinoline, 2-dimethylquinoline, and at least one of the ethyl esters of furan.
The ester-based solvent may be selected from, but is not limited to, alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. At least one of octyl octanoate, diethyl sebacate, diallyl phthalate and isononyl isononanoate is particularly preferable.
The aromatic ketone-based solvent may be selected from, but is not limited to, 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof. Among them, the derivative may be selected from, but not limited to, at least one of 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropophenone, 3-methylpropophenone, and 2-methylpropophenone, as an example.
The aromatic ether-based solvent may be selected from, but is not limited to, at least one of 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylben-ther, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran and ethyl-2-naphthyl ether.
The aliphatic ketone-based solvent may be selected from, but is not limited to, 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as at least one of 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 and tetraethylene glycol dimethyl ether.
It is understood that the organic solvents may be used alone or as a mixed solvent of two or more organic solvents.
In some embodiments, the compositions of the present application include at least one boron-containing organic compound or mixture as described above, and at least one organic solvent, and may further include another organic solvent.
The other organic solvent may be selected from, but is not limited to, at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, 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, dimethylsulfoxide (DMSO), tetrahydronaphthalene, decalin, and indene.
In some embodiments, an organic solvent suitable for the present application is a solvent having Hansen (Hansen) solubility parameters within the following ranges: δd (dispersion force) is in the range of 17.0 to 23.2MPa1/2, particularly in the range of 18.5 to 21.0MPa 1/2;
δp (polar force) is in the range of 0.2 to 12.5MPa1/2, especially in the range of 2.0 to 6.0MPa 1/2;
δh (hydrogen bonding force) is in the range of 0.9 to 14.2MPa1/2, especially in the range of 2.0 to 6.0MPa 1/2.
In some embodiments, the organic solvent is selected with consideration of boiling point in the composition according to the present application. In at least some embodiments, the organic solvent has a boiling point of ∈deg.C or greater; preferably not less than 180 ℃; preferably not less than 200 ℃; more preferably not less than 250 ℃; the optimal temperature is more than or equal to 300 ℃. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads.
It is understood that the organic solvent may be evaporated from the solvent system to form a film comprising the organic compound.
In some embodiments, the composition is a solution. In still other embodiments, the composition is a suspension. The solution or suspension may additionally include additives for adjusting viscosity, adjusting film forming properties, improving adhesion, etc. The additive may be selected from at least one of, but not limited to, a surface active compound, a lubricant, a wetting agent, a dispersing agent, a hydrophobizing agent, and a binder.
The content of the boron-containing organic compound or mixture in the composition is 0.01 to 10wt%, preferably 0.1 to 5wt%, more preferably 0.2 to 5wt%, most preferably 0.25 to 3wt%.
The application also relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device. In some embodiments, the composition is used to prepare organic electronic devices by a print or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roller printing, offset printing, flexography, rotary printing, spray coating, brush coating, pad printing, slot die coating, and the like. Preferred are gravure printing, inkjet printing and inkjet printing.
The present application also relates to the use of a boron-containing organic compound, mixture or composition as described above in an organic electronic device. The specific scheme is as follows:
an organic electronic device includes at least one organic functional layer. The organic functional layer comprises at least one boron-containing organic compound or mixture as described above, or the organic functional layer is prepared from the composition as described above.
Further, the organic electronic device includes a cathode, an anode, and at least one organic functional layer. The organic functional layer comprises at least one boron-containing organic compound or mixture as described above, or the organic functional layer is prepared from the composition as described above. The organic functional layer may be, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an electron blocking layer, an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), or a Hole Blocking Layer (HBL). In at least one embodiment, the organic functional layer is a light emitting layer.
The organic electronic device may be, but is 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, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emitting diode (Organic Plasmon Emitting Diode), and the like. Organic electroluminescent devices such as OLEDs and organic light emitting field effect transistors are particularly preferred. Further particularly preferred are OLEDs.
In one embodiment, the organic electronic device includes a substrate, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode sequentially stacked on the substrate. The light-emitting layer comprises at least one organic compound or mixture as described above, or the light-emitting layer is prepared from a composition as described above. It is understood that the structure of the organic electronic device is not limited thereto.
The substrate may be transparent or opaque. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. The substrate is preferably a substrate having a smooth surface, and a substrate free of surface defects is a particularly desirable choice. In one embodiment, the substrate is flexible and the material may be selected from, but is not limited to, a polymer film or plastic having a glass transition temperature Tg of 150℃or higher, preferably 200℃or higher, more preferably 250℃or higher, and most preferably 300℃or higher. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode is an electrode that injects holes, and the anode can easily inject holes into a hole injection layer, or a hole transport layer, or a light emitting layer. The anode may comprise a conductive metal, conductive metal oxide, or conductive polymer. In one embodiment, the work function of the anode and the HOMO energy level or valence band energy of the emitter in the light-emitting layer or of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL)The absolute value of the difference in order is less than 0.5eV, preferably less than 0.3eV, and 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 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 patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application. The cathode is an electrode injecting electrons, and the cathode can easily inject electrons into an electron injection layer, or an electron transport layer, or a 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 or conduction band level of the light-emitting body in the light-emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials that can be used as cathodes for organic electronic devices are possible as cathode materials for the devices of the present invention. Examples of cathode materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF 2 /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 hole injection layer is a layer for promoting injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can receive holes injected from the positive electrode proficiently 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. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, polyaniline-based and polythiophene-based conductive polymer, and the like, but are not limited thereto.
The hole transport layer may be used to smoothly transport holes. The hole transport material for the hole transport layer known in the art is suitably a material having high hole mobility, which can receive holes transported from the anode or the hole injection layer and transfer the holes to the light emitting layer. Specific examples thereof include an arylamine-based organic material, a carbazole-based organic material, a conductive polymer, a block copolymer having both a conjugated portion and a non-conjugated portion, 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. As the electron blocking layer, a spiroindoloacridine-based compound or a material known in the art may be used.
The electron transport layer may be used to smoothly transport electrons. The electron transport material is suitably a material having high electron mobility, which can be proficiently receiving electrons injected from the negative electrode and transferring the electrons to the light emitting layer. Specific examples thereof may include, but are not limited to: at least one of Al complexes of 8-hydroxyquinoline, complexes comprising Alq3, organic radical compounds, hydroxyflavone-metal complexes, lithium 8-hydroxyquinoline (LiQ), and benzimidazole-based compounds.
The electron injection layer may be used to smoothly inject electrons. The electron injection material is preferably: has an ability to transport electrons, has an effect of injecting electrons from the negative electrode, has an excellent effect of injecting electrons into the light emitting layer or the light emitting material, prevents excitons generated by the light emitting layer from moving to the hole injecting layer, and also has an excellent ability to form a thin film. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone and the like and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like, but are not limited thereto.
It will be appreciated that the organic electronic device may further comprise a hole blocking layer between the light emitting layer and the electron transporting layer, which is a layer that blocks holes from reaching the negative electrode, and may be generally formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, diazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like.
The organic electronic device has a luminescence wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm.
In one embodiment, the organic electronic device described herein is a solution-type organic electronic device, one or more functional layers of which are prepared by printing; further, the solution-type organic electronic device is a solution-type OLED.
The invention also relates to the use of an organic electronic device according to the invention in various electronic devices, which may be, but are not limited to, display devices, lighting devices, light sources, sensors, etc.
The application also relates to an electronic device comprising said electronic device. The electronic device may be, but is not limited to, a display device, a lighting device, a light source, a sensor, etc.
The present application is specifically illustrated by the following examples, which are only some of the examples of the present application and are not limiting of the present application.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
The synthetic route for the organic compound 1 of this example is as follows:
synthesis of intermediate 1-3:
under the protection of nitrogen, 20mmol of intermediate 1-1, 10mmol of intermediate 1-2, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 1-3 is purified by using a flash column chromatography method, so that the yield is 81.5%. MS (ASAP) =446.
Synthesis of intermediates 1-5:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 1-3, 10mmol of intermediate 1-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin drying to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 1-5, wherein the yield is 86.4%. MS (ASAP) =503.
Synthesis of intermediates 1-7:
under the protection of nitrogen, 20mmol of intermediate 1-5, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 1-7 is purified by using a flash column chromatography method, so that the yield is 59.4%. MS (ASAP) =1170.
Synthesis of organic compound 1:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 1-7 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellow-green solid, namely organic compound 1, was obtained by column chromatography (eluent PE) in 60.5% yield, MS (ASAP) =1186.
Example 2
The synthetic route for the organic compound 2 of this example is as follows:
Synthesis of intermediate 2-2:
under the protection of nitrogen, 20mmol of intermediate 2-1, 10mmol of intermediate 1-2, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 2-2 is purified by using a flash column chromatography method, so that the yield is 70.4%. MS (ASAP) =750.
Synthesis of intermediate 2-4:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 2-2, 10mmol of intermediate 2-3, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 2-4 with the yield of 66.8%. MS (ASAP) =883.
Synthesis of intermediate 2-5:
under the protection of nitrogen, 20mmol of intermediate 2-4, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 2-5 is purified by using a flash column chromatography method, so that the yield is 54.7%. MS (ASAP) =1930.
Synthesis of organic compound 2:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 2-5 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the flask cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, the organic compound 2 was obtained as a yellowish green solid by column chromatography (eluent PE) in 43.8% yield, MS (ASAP) =1946.
Example 3
The synthetic route for the organic compound 3 of this example is as follows:
Synthesis of intermediate 3-2:
under the protection of nitrogen, 20mmol of intermediate 3-1, 10mmol of intermediate 1-2, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 3-2 is purified by using a flash column chromatography method, so that the yield is 72.6%. MS (ASAP) =646.
Synthesis of intermediate 3-4:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 3-2, 10mmol of intermediate 3-3, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases which are washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying the obtained intermediate 3-4 by using a flash column chromatography method, wherein the yield is 67.1%. MS (ASAP) =753.
Synthesis of intermediate 3-5:
under the protection of nitrogen, 20mmol of intermediate 3-4, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask under the protection of nitrogen, 150ml of toluene is added to dissolve the mixture, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out on the solvent to obtain a crude mouth, and the intermediate 3-5 is purified by using a flash column chromatography method, so that the yield is 57.6%. MS (ASAP) =1670.
Synthesis of organic compound 3:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 3-5 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellowish green solid was obtained by column chromatography (eluent PE), i.e. organic compound 3, yield 61.7%, MS (ASAP) =1686.
Example 4
The synthetic route for the organic compound 4 of this example is as follows:
Synthesis of intermediate 4-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 4-1, 10mmol of intermediate 1-2, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 4-2 with the yield of 85.2%. MS (ASAP) =670.
Synthesis of intermediate 4-4:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 4-2, 10mmol of intermediate 4-3, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 4-4 with the yield of 63.7%. MS (ASAP) =783.
Synthesis of intermediate 4-5:
under the protection of nitrogen, 20mmol of intermediate 4-4, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 4-5 is purified by using a flash column chromatography method to obtain the yield of 52.4%. MS (ASAP) =1731.
Synthesis of organic compound 4:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 4-5 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellow-green solid, i.e. organic compound 4, was obtained by column chromatography (eluent PE) in 39.6% yield, MS (ASAP) =1747.
Example 5
The synthetic route for the organic compound 5 of this example is as follows:
Synthesis of intermediate 5-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 4-4, 10mmol of intermediate 5-1, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 5-2, wherein the yield is 74.8%. MS (ASAP) =1717.
Synthesis of organic compound 5:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 5-2 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellow-green solid, namely organic compound 5, was obtained by column chromatography (eluent PE) in 46.9% yield, MS (ASAP) =1733.
Example 6
The synthetic route for the organic compound 6 of this example is as follows:
Synthesis of intermediate 6-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 4-4, 10mmol of intermediate 6-1, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 6-2, wherein the yield is 75.9%. MS (ASAP) =1747.
Synthesis of organic compound 6:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 6-2 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellow-green solid, i.e. organic compound 6, was obtained by column chromatography (eluent PE) in 50.3% yield, MS (ASAP) =1763.
Example 7
The synthetic route for the organic compound 7 of this example is as follows:
Synthesis of intermediate 7-2:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 4-4, 10mmol of intermediate 7-1, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 7-2 is purified by using a flash column chromatography method, so that the yield is 67.5%. MS (ASAP) =1744.
Synthesis of organic compound 7:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 7-2 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, a yellow-green solid, namely organic compound 7, was obtained by column chromatography (eluent PE) in 44.8% yield, MS (ASAP) =1760.
Example 8
The synthetic route for the organic compound 8 of this example is as follows:
Synthesis of intermediate 8-3:
preparing a dry 500mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; the nitrogen circulation is kept in the reaction bottle, 10mmol of intermediate 8-1, 10mmol of intermediate 8-2, 30mmol of cesium carbonate and 200ml of DMF are added, the vacuum pumping and nitrogen introducing are carried out for three times, and the temperature is raised to 120 ℃; after 12h of reaction, extract with DCM, spin-dry the solvent and obtain intermediate 8-3 by column chromatography (eluent PE) in 62.4% yield, MS (ASAP) =295.
Synthesis of intermediate 8-5:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 8-3, 10mmol of intermediate 8-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 8-5, wherein the yield is 56.7%. MS (ASAP) =413.
Synthesis of intermediate 8-7:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 8-5, 10mmol of intermediate 8-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 8-7, wherein the yield is 73.5%. MS (ASAP) =484.
Synthesis of intermediate 8-8:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 8-7, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 8-8 is purified by using a flash column chromatography method to obtain the yield of 52.7%. MS (ASAP) =1132.
Synthesis of organic compound 8:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 8-8 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, the organic compound 8 was obtained as a yellowish green solid by column chromatography (eluent PE) in a yield of 50.9%, MS (ASAP) =1148.
Example 9
The synthetic route for the organic compound 9 of this example is as follows:
Synthesis of intermediate 9-3:
preparing a dry 500mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; the nitrogen circulation is kept in the reaction bottle, 20mmol of intermediate 9-1, 10mmol of intermediate 9-2, 50mmol of cesium carbonate and 200ml of DMF are added, the vacuum pumping and nitrogen introducing are carried out for three times, and the temperature is raised to 120 ℃; after 12h of reaction, extract with DCM, spin-dry the solvent and use column chromatography (eluent PE) to intermediate 9-3 in 84.2% yield, MS (ASAP) =424.
Synthesis of intermediate 9-5:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 9-3, 10mmol of intermediate 9-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 9-5, wherein the yield is 71.7%. MS (ASAP) =479.
Synthesis of intermediate 9-6:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 9-5, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and spin-evaporation are carried out to obtain a crude mouth, and the intermediate 9-6 is purified by using a flash column chromatography method, so that the yield is 78.1%. MS (ASAP) =1122.
Synthesis of organic compound 9:
preparing a dried 100mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; maintaining nitrogen circulation in the reaction bottle, adding 10mmol of intermediate 9-6 and 20ml of toluene, vacuumizing, introducing nitrogen, circulating for three times, and heating to 120 ℃; to the reaction flask was slowly added dropwise 20mmol of boron tri-iodide, the cap was screwed down, after 12h of reaction, the mixture was extracted with DCM, and after spin-drying the solvent, the organic compound 9 was obtained as a yellowish green solid by column chromatography (eluent PE) in a yield of 32.7%, MS (ASAP) =1139.
Example 10
The synthetic route for the organic compound 10 of this example is as follows:
synthesis of intermediate 10-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 10-1, 10mmol of intermediate 8-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 10-2 with the yield of 58.5%. MS (ASAP) =341.
Synthesis of intermediate 10-3:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 10-2, 10mmol of intermediate 8-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 10-3, wherein the yield is 67.5%. MS (ASAP) =412.
Synthesis of intermediate 10-4:
under the protection of nitrogen, 20mmol of intermediate 10-3, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the mixture, the mixture is heated to 110 ℃ until the reaction solution is refluxed for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and spin-drying of the solvent are carried out to obtain a crude mouth, and the intermediate 10-4 is purified by using a flash column chromatography method, so that the yield is 63.8%. MS (ASAP) =988.
Synthesis of organic compound 10:
into a 250ml three-necked flask, 10mmol of intermediate 10-4 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, organic compound 10, 29.4% yield, MS (ASAP) =936.
Example 11
The synthetic route for the organic compound 11 of this example is as follows:
synthesis of intermediate 11-3:
preparing a dry 500mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; the nitrogen circulation is kept in the reaction bottle, 10mmol of intermediate 11-1, 10mmol of intermediate 11-2, 50mmol of cesium carbonate and 200ml of DMF are added, the vacuum pumping and nitrogen introducing are carried out for three times, and the temperature is raised to 120 ℃; after 12h of reaction, extract with DCM, spin-dry the solvent and obtain intermediate 11-3 by column chromatography (eluent PE) in 86.1% yield, MS (ASAP) =266.
Synthesis of intermediate 11-4:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 11-3, 10mmol of intermediate 8-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 11-4 with the yield of 60.8%. MS (ASAP) =351.
Synthesis of intermediate 11-5:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 11-4, 10mmol of intermediate 1-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 11-5 is purified by using a flash column chromatography method to obtain the yield of 73.6%. MS (ASAP) =866.
Synthesis of organic compound 11:
into a 250ml three-necked flask, 10mmol of intermediate 11-5 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, i.e., organic compound 11, in 34.7% yield, MS (ASAP) =814.
Example 12
The synthetic route for the organic compound 12 of this example is as follows:
synthesis of intermediate 12-1:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 10-1, 10mmol of intermediate 1-1, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 12-1, wherein the yield is 84.6%. MS (ASAP) =313.
Synthesis of intermediate 12-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 12-1, 10mmol of intermediate 1-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 12-2 with the yield of 63.3%. MS (ASAP) =370.
Synthesis of intermediate 12-4:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 12-2, 10mmol of intermediate 12-3, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and spin-drying of the solvent are carried out to obtain a crude mouth, and the intermediate 12-4 is purified by using a flash column chromatography method to obtain the yield of 57.9%. MS (ASAP) =949.
Synthesis of organic compound 12:
into a 250ml three-necked flask, 10mmol of intermediate 12-4 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, i.e., organic compound 12, in 33.8% yield, MS (ASAP) =897.
Example 13
The synthetic route for the organic compound 13 of this example is as follows:
synthesis of intermediate 13-3:
preparing a dry 500mL schlenk bottle, setting up a reaction device, vacuumizing, and introducing nitrogen; the nitrogen circulation is kept in the reaction bottle, 10mmol of intermediate 13-1, 10mmol of intermediate 13-2, 50mmol of cesium carbonate and 200ml of DMF are added, the vacuum pumping and nitrogen introducing are carried out for three times, and the temperature is raised to 120 ℃; after 12h of reaction, extract with DCM, spin-dry the solvent and obtain intermediate 13-3 by column chromatography (eluent PE) in 75.2% yield, MS (ASAP) =325.
Synthesis of intermediate 13-5:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 13-3, 20mmol of intermediate 13-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases which are washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 13-5, wherein the yield is 87.8%. MS (ASAP) =352.
Synthesis of intermediate 13-8:
10mmol of intermediate 13-6, 20mmol of intermediate 13-7 and 0.2 mmole Pd (PPh) are respectively added into a dry three-neck flask under the protection of nitrogen 3 ) 4 1.38 g of potassium carbonate is dissolved by adding 150ml of 1,4 dioxane, heating to 90 ℃ until the reaction liquid flows back, reacting for 12 hours, after the reaction is complete, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude port, and purifying by using a flash column chromatography to obtain the intermediate 13-8 with the yield of 82.6 percent. MS (ASAP) =333.
Synthesis of intermediate 13-10:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 13-8, 10mmol of intermediate 13-9, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases which are washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying the crude mouth by using a flash column chromatography method to obtain the intermediate 13-10 with the yield of 63.4%. MS (ASAP) =555.
Synthesis of intermediate 13-11:
under the protection of nitrogen, 20mmol of intermediate 13-10, 10mmol of intermediate 13-5, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the mixture, the mixture is heated to 110 ℃ until the reaction solution is refluxed for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and spin-drying of the solvent are carried out to obtain a crude mouth, and the intermediate 13-11 is obtained through purification by using a flash column chromatography method, wherein the yield is 39.4%. MS (ASAP) =1302.
Synthesis of intermediate 13-12:
under the protection of nitrogen, 10mmol of intermediate 13-11, 20mmol of intermediate 13-8, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added into a dry three-neck flask, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and spin-drying of the solvent are carried out to obtain a crude mouth, and the intermediate 13-12 is purified by using a flash column chromatography method to obtain the product with the yield of 83.6%. MS (ASAP) =1897.
Synthesis of organic compound 13:
into a 250ml three-necked flask, 10mmol of intermediate 13-12 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, i.e. organic compound 13, in 34.7% yield, MS (ASAP) =1845.
Example 14
The synthetic route for the organic compound 14 of this example is as follows:
synthesis of intermediate 14-3:
in a dry three-neck flask under the protection of nitrogen, 10mmol of intermediate 14-1, 10mmol of intermediate 14-2, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 14-3 is purified by using a flash column chromatography method, so that the yield is 82.1%. MS (ASAP) =487.
Synthesis of intermediate 14-5:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 14-3, 10mmol of intermediate 14-4, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 14-5, wherein the yield is 62.9%. MS (ASAP) =614.
Synthesis of intermediate 14-7:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 14-5, 10mmol of intermediate 14-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the intermediate, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 14-7 is purified by using a flash column chromatography method, so that the yield is 52.3%. MS (ASAP) =1378.
Synthesis of intermediate 14-8:
in a dry three-neck flask under the protection of nitrogen, 20mmol of intermediate 14-1, 10mmol of intermediate 14-7, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate are respectively added, 150ml of toluene is added to dissolve the two, the mixture is heated to 110 ℃ until the reaction liquid flows back, the reaction is carried out for 12 hours, water is added to carry out extraction and deactivation reaction, simultaneously, dichloromethane is used for extracting an organic phase, the organic phase is combined for multiple times, anhydrous magnesium sulfate is used for drying, filtration and rotary evaporation are carried out to obtain a crude mouth, and the intermediate 14-8 is purified by using a flash column chromatography method, so that the yield is 53.6%. MS (ASAP) =1925.
Synthesis of organic compound 14:
into a 250ml three-necked flask, 10mmol of intermediate 14-8 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, i.e., organic compound 14, in 38.6% yield, MS (ASAP) =1873.
Example 15
The synthetic route for the organic compound 15 of this example is as follows:
synthesis of intermediate 15-2:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 15-1, 10mmol of intermediate 13-9, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ until the reaction liquid flows back, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple times of washing the organic phase, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 15-2, wherein the yield is 83.9%. MS (ASAP) =428.
Synthesis of intermediate 15-4:
in a dry three-neck flask under the protection of nitrogen, respectively adding 10mmol of intermediate 15-2, 10mmol of intermediate 15-3, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the mixture, heating to 110 ℃ until the reaction solution is refluxed, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, combining multiple washing organic phases, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 15-4, wherein the yield is 89.8%. MS (ASAP) =504.
Synthesis of intermediate 15-6:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 15-4, 10mmol of intermediate 15-5, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ to reflux the reaction solution, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases which are washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 15-6, wherein the yield is 43.2%. MS (ASAP) =1185.
Synthesis of intermediate 15-8:
in a dry three-neck flask under the protection of nitrogen, respectively adding 20mmol of intermediate 15-7, 10mmol of intermediate 15-6, 0.2mmol of palladium acetate, 0.2mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate, adding 150ml of toluene to dissolve the intermediate, heating to 110 ℃ to reflux the reaction solution, reacting for 12 hours, adding water to extract and kill the reaction, simultaneously extracting an organic phase with dichloromethane, merging the organic phases which are washed for multiple times, drying with anhydrous magnesium sulfate, filtering, evaporating the solvent by spin to obtain a crude mouth, and purifying by using a flash column chromatography to obtain the intermediate 15-8, wherein the yield is 74.6%. MS (ASAP) =1651.
Synthesis of organic compound 15:
into a 250ml three-necked flask, 10mmol of intermediate 15-8 and 100ml of dried tert-butylbenzene were charged and introduced into N 2 In the atmosphere, cooled to-30℃and a solution of t-BuLi (t-butyllithium) in n-hexane was added dropwise (42 mmol). The reaction was carried out at a temperature of 60℃for 2 hours, and the n-hexane solvent was distilled off under reduced pressure. The reaction solution was cooled again to-30 ℃, 42mmol of boron tribromide solution was added, stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 ℃, 64mmol of N, N-diisopropylethylamine was added, after the dropwise addition was completed, stirred at room temperature, then stirred at room temperature again at 120 ℃ for 3 hours, and the reaction solution was cooled to room temperature. The reaction was quenched by adding aqueous sodium carbonate and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the organic phases are combined, the solvent in the organic phases is distilled off in a rotary way, crude products are obtained, and the crude products are purified by a rapid silica gel column to obtain pure products. Recrystalization with toluene and ethyl acetate gives the product as a pale yellow solid powder, i.e. organic compound 15, in 32.1% yield, MS (ASAP) =1599.
Comparative example
The organic compound of this comparative example is BD-Ref1, which has the following chemical structural formula:
the energy levels HOMO, LUMO, T1 and S1 of the boron-containing organic compounds of examples 1 to 15 and the comparative compound BD-Ref1 of the comparative example were obtained by quantum computation. Specifically, using TD-DFT (time-density functional theory) through Gaussian09W (Gaussian inc.), a specific simulation method can be seen in WO2011141110, first, the molecular geometry is optimized by a Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin single let), then the energy structure of the organic molecule is calculated by the TD-DFT (time-density functional theory) method as "TD-SCF/DFT/Default Spin/B3PW91" and the group "6-31G (d)" (Charge 0/Spin single let), and the HOMO and LUMO energy levels are calculated according to the following calibration formulas, and S1 and T1 are directly used.
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
HOMO, LUMO, T1 and S1 are direct calculations of Gaussian09W, in Hartree, and are shown in Table one.
Table one:
as can be seen from Table one, the T1 energy level and S1 energy level of the boron-containing organic compounds 1 to 15 of examples 1 to 15 of the present application are both significantly higher than those of the comparative compound BD-Ref1 of the comparative example.
OLED device was prepared:
in the OLED device of this embodiment, ITO is used as the anode, and PEDOT (polyethylene dioxythiophenes, clevelos TM AI 4083) as a hole injection layer material, PVK (Sigma Aldrich, average Mn 25,000 ～ 50,000) as a hole transport material, BH as a host material for a light emitting material, BD-Ref1 in examples 1 to 12 as guest materials for a light emitting material, ET and Liq (8-hydroxyquinoline lithium) as electron transport materials, and Al as a cathode, and the device structure of ITO/PEDOT/PVK/BH: organic compound/ET: liq/Al was constituted.
A schematic diagram of an OLED device is shown in fig. 1. Wherein 10 is a substrate, 20 is an anode, 30 is a hole injection layer, 40 is a hole transport layer, 50 is a light emitting layer, 60 is an electron transport layer, and 70 is a cathode.
The chemical structural formula of BH, ET, liq is as follows:
the BH, ET, liq, BD-Ref1 is commercially available or the synthetic methods are known in the art.
The process of manufacturing an OLED device using the above materials is described in detail below by way of specific examples.
Device example 1
The method for manufacturing the OLED device of the present embodiment includes the steps of:
a. cleaning of an ITO (indium tin oxide) anode layer: washing the ITO conductive glass by using chloroform, acetone and/or isopropanol, and then carrying out ultraviolet ozone treatment;
b. forming a hole injection layer: spin-coating a hole injection layer material PEDOT (polyethylene dioxythiophene, clevelos) on the ITO anode layer TM AI 4083) and treated on a hot plate at 180 ℃ for 10 minutes, the hole injection layer thickness was 40nm;
c. forming a hole transport layer: a toluene solution of PVK (Sigma Aldrich, average Mn25,000-50,000) at a concentration of 5mg/ml was spin-coated on the hole injection layer, followed by treatment on a hot plate at 180℃for 60 minutes, the thickness of the hole transport layer being 20nm;
d. forming a light emitting layer: in a nitrogen glove box, spin-coating a luminescent layer material on a hole transport layer, and then processing the luminescent layer material on a hot plate at 140 ℃ for 10 minutes, wherein a host material of the luminescent layer material is BH, a guest material is the organic compound 1 in the embodiment 1, a solvent is a methyl benzoate solution, the mass ratio of the host material to the guest material is 95:5, the concentration of the luminescent layer material is 15mg/ml, and the thickness of the luminescent layer is 40nm.
e. Forming an electron transport layer: ET and Liq are placed in different evaporation units, above the light emitting layer, in a vacuum chamber, under a high vacuum (1×10 -6 Millibar) to co-deposit ET and Liq in a weight ratio of 50:50 to form an electron transport layer having a thickness of 20nm;
f. forming a cathode layer: depositing Al on the electron transport layer to obtain an Al cathode with the thickness of 100 nm;
g. and (3) packaging: the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.
Device examples 2 to 15
Substantially the same as device example 1, except that the guest materials of the light-emitting layers of device examples 2 to 15 were selected from the organic compounds of examples 2 to 15, respectively.
Device comparative example
Substantially the same as in device example 1, except that the guest material of the light-emitting layer of the device comparative example was an organic compound BD-Ref1.
Performance detection and results
The current-voltage (J-V) characteristics of the OLED devices of device examples 1-15 and comparative example were tested using a characterization apparatus while recording the luminous efficiency and lifetime LT95@1000nits. Wherein the luminous efficiency is that the current density is 10mA/cm 2 The relative values obtained at that time; lifetime lt95@1000nits refers to the time at which the brightness of the device drops from an initial brightness of 1000nits to 95% of the initial brightness at a constant current. The test results are shown in Table II below.
And (II) table:
as can be seen from table two, the OLED devices of examples 1 to 15 of the present application have more excellent luminous efficiency and lifetime than OLED-Ref 1. Wherein, compared with the OLED device prepared by using the organic compound BD-Ref1 of the comparative example as the guest material in the light-emitting layer, the efficiency of the OLED device prepared by using the organic compounds 1-15 of examples 1-15 as the guest material in the light-emitting layer is generally improved by 9-64%, and the life (LT95@1000nits) of the OLED device is generally improved by 3-60%.
The whole molecular structure of the boron-containing organic compound has better conjugation and planarity, so that the rigidity and stability of the organic compound molecule are improved; meanwhile, the molecular structure can increase the number of solubilizing groups, so that the solubility of organic compound molecules is improved, compared with the organic compound BD-Ref1 in the comparative example, the solubility of the organic compound in the examples 1-15 is generally improved by 6-59%, on one hand, the boron-containing organic compound is easier to purify, so that the purity of the organic compound is improved, and the purposes of improving the luminous efficiency of a device and prolonging the service life of the device are further achieved; on the other hand, the solution processing device is easier to prepare, and the film forming uniformity of the film is improved.
The boron-containing organic compounds, mixtures, compositions and organic electronic devices provided in the examples of the present application are described in detail above, and specific examples are used herein to illustrate the principles and embodiments of the present application, the above examples being provided only to assist in understanding the methods of the present application and the core ideas thereof; meanwhile, those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, and the present description should not be construed as limiting the present application in view of the above.

Claims (11)

1. A boron-containing organic compound having a structure represented by the general formula (1-1) or the general formula (1-2):
wherein:
X 1 、X 3 、X 5 、X 6 each independently selected from NR 1 、O，X 2 、X 4 Each independently selected from NR 1 O, S, se or none;
Ar 1 -Ar 9 each independently selected from a substituted or unsubstituted aromatic group having 6 to 30C atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms;
a is selected from single bond, NR 1 、O、S；
R 1 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, a linear thioalkoxy 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 branched chain having 3 to 20C atomsAlkoxy, or cyclic alkoxy having 3 to 20C atoms, branched thioalkoxy having 3 to 20C atoms, or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, alkylene having 1 to 20C atoms, -CN, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxy, nitro, -CF 3 -Cl, -Br, -F, an aromatic group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaromatic group having 5 to 30 ring atoms substituted or unsubstituted, an aryloxy group having 6 to 30 ring atoms substituted or unsubstituted, a heteroaryloxy group having 5 to 30 ring atoms substituted or unsubstituted, or a combination of these groups;
when a defined group is substituted, the defined group may be substituted with one or more substituents independently selected from the group consisting of: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl.
2. The boron-containing organic compound according to claim 1, wherein the boron-containing organic compound is selected from any one of structures represented by general formulae (2-1) to (2-3):
3. the boron-containing organic compound according to claim 1 or 2, wherein Ar 1 -Ar 2 、Ar 5 -Ar 9 Each occurrence is independently selected fromOne or a combination of several structures represented by the formulas (B-1) to (B-7):
wherein:
x is independently selected from CR for each occurrence 2 ；
Y is independently selected from NR at each occurrence 3 S or O;
R 2 、R 3 each occurrence is independently selected from: -H, -D, linear alkyl having 1 to 20C atoms, linear alkoxy having 1 to 20C atoms, linear thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy 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, hydroxyl, nitro, amino, -CF 3 -Cl, -Br, -F, a substituted or unsubstituted aromatic group having 6 to 20C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups;
When a defined group is substituted, the defined group may be substituted with one or more substituents independently selected from the group consisting of: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1 to 20C atoms, heterocyclyl containing 3 to 20 ring atoms, aromatic containing 6 to 20 ring atoms, heteroaromatic containing 5 to 20 ring atoms, silane, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, haloformyl, formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl.
4. The boron-containing organic compound according to claim 3, wherein the boron-containing organic compound is selected from any one of structures represented by general formulae (3-1) to (3-6):
wherein R represents a substituent.
5. The boron-containing organic compound according to claim 4, wherein the structure of the boron-containing organic compound is selected from any one of structures represented by general formulae (4-1) to (4-7):
wherein Z is independently selected from NR for each occurrence 1 O or S.
6. The boron-containing organic compound according to claim 5,
X 1 、X 3 、X 5 、X 6 each independently selected from NR 4 、O，X 2 、X 4 Each independently selected from NR 4 O, S, se or none;
R 4 、Ar 8 and Ar is a group 9 Each independently selected from the following structures:
x is independently selected from CR for each occurrence 5 ；
R 5 Each occurrence is independently selected from: -H, -D, a linear alkyl group having 1 to 20C atoms, a branched or cyclic alkyl group having 3 to 20C atoms, an aromatic group having 6 to 20C atoms, or a combination of these groups.
7. The boron-containing organic compound according to claim 6, wherein R 4 、Ar 8 And Ar is a group 9 Each independently selected from the following structures:
8. the boron-containing organic compound of claim 7, wherein the boron-containing organic compound is selected from the following structures:
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9. a mixture characterized by: the mixture comprising the boron-containing organic compound according to any one of claims 1 to 8 and at least one organic functional material selected from a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting guest material, a light emitting host material or an organic dye.
10. A composition characterized by: the composition comprising the boron-containing organic compound of any one of claims 1 to 8 or the mixture of claim 9 and at least one organic solvent.
11. An organic electronic device comprising at least one organic functional layer, characterized in that: the organic functional layer comprises the boron-containing organic compound according to any one of claims 1 to 8, or the mixture according to claim 9, or is prepared from the composition according to claim 10.
CN202310128781.1A 2023-02-07 2023-02-07 Boron-containing organic compounds, mixtures, compositions and organic electronic devices Pending CN117466921A (en)

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