阅读说明：本技术 吲哚并[3,2,1-kl]吩噁嗪化合物、其制备方法与应用以及电子器件 (Indolo [3,2,1-kl ] phenoxazine compound, preparation method and application thereof, and electronic device ) 是由 廖良生 蒋佐权 朱向东 于 2020-07-02 设计创作，主要内容包括：本发明提供一种吲哚并[3,2,1-kl]吩噁嗪化合物、其应用以及电子器件。本发明的吲哚并[3,2,1-kl]吩噁嗪化合物通过引入吲哚并[3,2,1-kl]吩噁嗪的刚性结构,其的成膜性和热稳定性优异,可用于制备有机电致发光器件、钙钛矿太阳能电池、有机场效应晶体管和有机太阳能电池。另外,本发明的吲哚并[3,2,1-kl]吩噁嗪化合物可以作为空穴注入层、空穴传输层、发光层、电子阻挡层、空穴阻挡层或电子传输层的构成材料,能够降低驱动电压,提高效率、亮度和寿命等。更为重要的是,本发明的吲哚并[3,2,1-kl]吩噁嗪化合物具有非常良好的平面性,因此可以高效地传输载流子,从而是构建空穴传输材料的理想骨架。本发明的吲哚并[3,2,1-kl]吩噁嗪化合物的制备方法简单,原料易得,能够满足工业化的发展需求。(The invention provides an indolo [3,2,1-kl ] phenoxazine compound, application thereof and an electronic device. According to the indolo [3,2,1-kl ] phenoxazine compound, by introducing the rigid structure of indolo [3,2,1-kl ] phenoxazine, the film forming property and the thermal stability of the compound are excellent, and the compound can be used for preparing organic electroluminescent devices, perovskite solar cells, organic field effect transistors and organic solar cells. In addition, the indolo [3,2,1-kl ] phenoxazine compound can be used as a constituent material of a hole injection layer, a hole transport layer, a luminescent layer, an electron blocking layer, a hole blocking layer or an electron transport layer, and can reduce driving voltage, improve efficiency, brightness, prolong service life and the like. More importantly, the indolo [3,2,1-kl ] phenoxazine compound has very good planarity, so that the indolo [3,2,1-kl ] phenoxazine compound can efficiently transmit carriers, and is an ideal framework for constructing a hole transport material. The preparation method of the indolo [3,2,1-kl ] phenoxazine compound is simple, raw materials are easy to obtain, and the industrial development requirement can be met.)

1. An indolo [3,2,1-kl ] phenoxazine compound characterized by being represented by the following general formula (1):

wherein R is₁、R₂And R₃Each independently selected from cyano, or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

z represents CR¹Or N;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃Substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkyl having 2 to 20 carbonsOne or more of an atomic alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R²represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

2. Indolo [3,2,1-kl ] according to claim 1]A phenoxazine compound characterized in that R is₁、R₂And R₃Each independently selected from cyano or from any one of the following general formulae Ar-1 to Ar-29:

wherein the wavy line represents a bond bonded to the mother nucleus of indolo [3,2,1-kl ] phenoxazine,

R¹have the meaning as defined in claim 1.

3. The indolo [3,2,1-kl ] according to any one of claims 1 to 3]Phenoxazine compounds, characterized in that R¹Represents phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenylboryl, triphenylphosphoxy, diphenylphosphiloxy, triphenylsilyloxyOr tetraphenylsilyl.

4. The indolo [3,2,1-kl ] phenoxazine compound of any of claims 1, wherein the indolo [3,2,1-kl ] phenoxazine compound is selected from any of the following general formulae 1-1 to 1-51:

5. an electronic device, characterized in that it comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the organic layer contains the indolo [3,2,1-kl ] phenoxazine compound according to any one of claims 1 to 4.

6. Use of the indolo [3,2,1-kl ] phenoxazine compound according to any one of claims 1 to 4 in an electronic device as a light emitting material, an electron transporting material, an electron blocking material, a hole injecting material or a hole blocking material.

7. Use according to claim 6, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, an organic solar cell or a perovskite solar cell.

8. Use of an indolo [3,2,1-kl ] phenoxazine compound according to any one of claims 1 to 4 in the preparation of a hole transport layer.

Technical Field

The invention relates to an indolo [3,2,1-kl ] phenoxazine compound, application thereof and an electronic device, and belongs to the technical field of organic photoelectric materials.

Background

Since 2009, perovskite solar cells (pescs) have attracted much attention and have been rapidly developed due to their wide and strong absorption band, long exciton diffusion distance, and high photoelectric conversion efficiency. The energy conversion efficiency of the perovskite cell device prepared based on the solution method at present has broken through 24% and the time for stable operation in the atmospheric environment has exceeded 1000 hours, and these results fully show the great potential of the perovskite solar cell.

The structure of the perovskite battery mainly comprises an active layer (perovskite layer), a hole transport layer and an electron transport layer. The hole transport layer functions to extract and transport holes and suppress carrier recombination. A hole transport layer having excellent properties is required to have a suitable energy level, a high hole transport ability, and a good thermal stability. Commonly used organic hole transport materials include spirofluorene derivatives, pyrene derivatives, conductive polymers. However, these commonly used hole transport materials typically have more complicated synthesis and purification steps with higher costs, thereby increasing commercial costs. Currently, indolo [3,2,1-kl ] phenoxazine compounds have been reported in the fields of organic light emitting diodes, dye-sensitized solar cells and the like due to their simple synthesis steps and excellent chemical properties. In order to further improve the efficiency of a perovskite solar cell from the perspective of a hole transport material and reduce the cost of the cell, a series of indolo [3,2,1-kl ] phenoxazine compounds which can be used as the hole transport material are obtained by taking the chemical structure of indolo [3,2,1-kl ] phenoxazine as a core and introducing an electron-donating group for modification.

Disclosure of Invention

The invention aims to provide a series of novel indolo [3,2,1-kl ] phenoxazine compounds which can be used as luminescent materials, electron transport materials, electron blocking materials, hole injection materials or hole blocking materials, and application of the indolo [3,2,1-kl ] phenoxazine compounds in preparation of organic electroluminescent devices, organic field effect transistors, organic solar cells and perovskite solar cells. The indolo [3,2,1-kl ] phenoxazine compound has simple and convenient synthesis and purification steps, and has matched energy level and higher hole mobility, so that the indolo [3,2,1-kl ] phenoxazine compound has higher electronic device efficiency when being applied to an organic electroluminescent device, an organic field effect transistor, an organic solar cell or a perovskite solar cell.

In order to achieve the purpose, the invention provides the following technical scheme: an indolo [3,2,1-kl ] phenoxazine compound is a compound comprising a compound represented by the following general formula (1):

wherein R is₁、R₂And R₃Each independently selected from cyano, or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

z represents CR¹Or N;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atomsOne or more of an alkynyl group of (a), a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R²represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

Further, said R at each position₁、R₂And R₃The groups are independently selected from any one of the following general formulas Ar-1 to Ar-29:

wherein the wavy line represents a bond bonded to the mother nucleus of indolo [3,2,1-kl ] phenoxazine,

R¹have the meaning as defined in claim 1.

Further, R¹And R²Independently represent one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron group, triphenyl phosphorus oxygen group, diphenyl phosphorus oxygen group, triphenyl silicon group, or tetraphenyl silicon group.

Further, the indolo [3,2,1-kl ] phenoxazine compound is selected from any one of the following general formulas 1-1 to 1-51:

the present invention also provides a method for preparing an indolo [3,2,1-kl ] phenoxazine compound according to the item, comprising the steps of:

indolo [3,2,1-kl ] functionalized by 3, 7 and 10 positions]Introduction of R by metal-catalyzed coupling reaction of phenoxazine compound₁、R₂And R₃A group.

Further, the electronic device is selected from an organic electroluminescent device, a perovskite solar cell, an organic field effect transistor or a perovskite solar cell.

The invention also provides an electronic device which is provided with the indolo [3,2,1-kl ] phenoxazine compound.

Further, the electronic device is a perovskite solar cell device, the perovskite solar cell device comprises an electron transport layer, a perovskite active layer and a hole transport layer, and the indolo [3,2,1-kl ] phenoxazine compound is arranged in the perovskite solar cell device.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, indolo [3,2,1-kl ] phenoxazine is used as a core, and various electron donating groups are modified on the core for regulation, so that the matching energy level, the high hole mobility and the high thermal stability can be obtained, and the high energy conversion efficiency is achieved. Compared with commercial spirobifluorene derivative material spirol-OMeTAD, the spirobifluorene derivative material has comparable energy conversion efficiency, wherein the device efficiency of spirobifluorene derivative material is not exceeded. Compared with spiro-OMeTAD, the method has simpler synthesis and purification steps, thereby greatly reducing the production cost and further reducing the cost.

The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.

Drawings

FIG. 1 is a graph showing ultraviolet absorption spectra (UV-Vis) and room temperature fluorescence spectra (PL) of compounds 1 to 21 and 1 to 9 in examples 1 and 2 of the present invention;

fig. 2 is a graph of current density versus voltage for the perovskite solar cell devices of examples 1 and 2 of the present invention and comparative example 1.

Detailed Description

The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

The invention provides an indolo [3,2,1-kl ] phenoxazine compound, which is a compound containing the following general formula (1):

wherein R is₁、R₂And R₃Each independently selected from cyano, or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

z represents CR¹Or N;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 carbon atomsOne or more of an aromatic heterocyclic group of an atom;

R²represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

<R₁And R₃>

R₁～R₃Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.

From R₁～R₃The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenylyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienyl, benzothiophenocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, perylenyl, pyranthrylyl, benzopyrenyl, pentacenyl, benzopyrenyl, terphenyl, Terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazoloimidazoleOxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzpyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazanthryl, diazperylenyl, tetraazaperylenyl, phthalazinyl, pyrazinyl, phenazinyl, phenothiazinyl, fluorescenzinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, benzoxazolyl, thiadiazolyl, phenothiazinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphinyloxy, diphenyl phosphinyloxy, triphenyl silyl, tetraphenyl silyl and the like.

In the present invention, preferably, R₁～R₃Each independently selected from a hydrogen atom, a cyano group or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R¹One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;

preferably, said R is₁、R₂And R₃Each independently selected from any one of the following general formulae Ar-1 to Ar-29:

wherein the wavy line represents a bond to the parent nucleus, R¹Have the meaning defined above.

From R₁～R₃Having 6 to 30 carbon atoms or having 5 to 30The aromatic heterocyclic group having a carbon atom may be unsubstituted, but may have a substituent. Preferably, from Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by¹Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

(R¹)

R¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃One or more of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R¹Alkyl having 1 to 20 carbon atoms represented by one or more of the following R²And (4) substitution.In addition, one or more non-adjacent CH in the alkyl group₂The group can be represented by R²C＝CR²、C≡C、Si(R²)₃、C＝O、C＝NR²、P(＝O)R²、SO、SO₂、NR²O, S or CONR²And wherein one or more hydrogen atoms may be replaced by deuterium atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R¹Substituents or two adjacent R²The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R²Substitution; where two or more substituents R¹May be connected to each other and may form a ring.

Preferably represented by R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphoxy, diphenyl phosphoxy, triphenyl silicon group, tetraphenyl silicon group, and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R²And (4) substitution.

(R²)

R²Represents one or more of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms represented by R¹The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.

From R²The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula¹The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.

(Z)

Z represents CR¹Or N, e.g. N, C-H, C-F, C-Cl, C-Br, C-I, C-CN, C-NO₂Carbon-phenyl, carbon-biphenyl, and the like.

R¹Have the meaning as defined above.

In a particularly preferred embodiment of the invention:

r of each bit₁、R₂And R₃Each of the groups is independently selected from the following aromatic or heteroaromatic ring systems: phenoxazinyl, phenothiazinyl, dianilino, triphenylamine, 9-dimethyl-10-phenyl-9, 10-dihydroacridinyl, 10-phenyl-10 hydro-phenothiazinyl; the aromatic or heteroaromatic ring system may be substituted by one or more R¹Substitution;

r at each position¹The groups are independently selected from: hydrogen, linear alkyl having 1 to 5C atoms.

Preferably, the compound is selected from any one of the following general formulae 1-1 to 1-51:

the invention also provides a preparation method of the indolo [3,2,1-kl ] phenoxazine compound, which comprises the following steps:

the compounds according to the invention can be prepared by synthetic procedures known to those of ordinary skill in the art, such as bromination, Suzuki coupling, buhward-Hartwig coupling, etc.

Synthesis of Compounds of the invention Indolo [3,2,1-kl ] functionalized typically from the 3, 7 and 10 positions]Starting with a phenoxazine compound, R is then introduced by a metal-catalyzed coupling reaction such as Suzuki coupling or Buhwald-Hardwald coupling₁、R₂And R₃A group.

In a preferred embodiment of the present invention, the indolo [3,2,1-kl]The phenoxazine compound is a halogen-functionalized compound, and R₁、R₂And R₃The group is derived from a boronic acid derivative functionalised compound.

In a second preferred embodiment of the present invention, the indolo [3,2,1-kl]The phenoxazine compound is a halogen functionalized compound, and is reacted with an amine derivative compound under the action of a palladium catalyst to introduce R₁、R₂And R₃A group. Among these, halogen functionalization is preferably bromination, chlorination, iodination, and particularly bromination.

In particular, in the first preferred embodiment described above, a boronic acid functionalized indolo [3,2,1-kl ] phenoxazine compound (intermediate M3) is prepared, and preferred preparation steps are exemplified below:

by controlling the reaction conditions, the yield of M1 can reach 80-95%, the yield of M2 can reach 70-95%, and the yield of M3 can reach 60-95%. After obtaining intermediate M3, an optional R is added to the system₁、R₂And R₃Reacting the boric acid functional compound of the group and a certain amount of palladium catalyst such as palladium tetrakis (triphenylphosphine), anhydrous potassium carbonate, toluene, ethanol and water at 80-120 ℃ for 20-35 hours under the protection of nitrogen, and finishing the reaction. Evaporating the solvent, dissolving the residue with dichloromethane and water, washing with water, separating organic layer, extracting water layer with dichloromethane, mixing organic layers, washing with water twice to neutrality, evaporating to remove solvent, separating by column chromatography, and drying to obtain the product. The molar ratio of intermediate M3 to tetrakis (triphenylphosphine) palladium is in the range of 15-20:1, preferably 18: 1; by adjusting the reaction conditions, the yield is 75-95%.

In the second preferred embodiment, M3 is preferably reacted with the amine derivative functionalized compound, tris (dibenzylideneacetone) dipalladium, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate and toluene are added into the system, and the reaction is completed at 90-120 ℃ for 10-30 hours under the protection of argon. And (4) carrying out suction filtration, decompressing, steaming to remove the solvent, carrying out column chromatography separation, and drying to obtain the product. The molar ratio of intermediate M3 to tris (dibenzylideneacetone) dipalladium is 15-20:1, preferably 18: 1; by adjusting the reaction conditions, the yield can reach 78-95%.

The invention also provides the application of the indolo [3,2,1-kl ] phenoxazine compound in preparing an electronic device, wherein the electronic device is selected from an organic electroluminescent device, a perovskite solar cell, an organic field effect transistor or a perovskite solar cell, and particularly provides the application of a hole transport material in preparing the perovskite solar cell.

The invention furthermore relates to electronic devices comprising at least one compound according to the invention. The electronic device is preferably selected from the group consisting of perovskite solar cells (PeSC), organic electroluminescent devices (organic light emitting diodes, OLEDs), organic field effect transistors (O-FETs), organic solar cells (O-SCs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic integrated circuits (O-ICs), Organic Dye Sensitized Solar Cells (ODSSC), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), organic laser diodes (O-lasers), organic plasma emitting devices and the like, preferably organic electroluminescent devices (OLEDs).

A PeSC generally comprises: substrates such as, but not limited to, glass, plastic, metal; an anode, such as a fluorine doped tin oxide (FTO) anode; an electron transport layer; a perovskite active layer; a hole transport layer; cathode modification layers, e.g. MoO₃(ii) a A cathode, such as Ag. However, it should be noted that there may be one or more layers per layer in between and that each layer need not be present.

The compound of the present invention may be used for any one or more layers of the device, but is preferably used for the hole transport layer because it has high hole mobility, suitable energy level, and good stability.

The hole transport layer dopant of the present invention is not particularly limited, but lithium bistrifluoromethanesulfonimide (Li-TFSI) and tetra-tert-butylpyridine (TBP) are preferable. To improve device performance, the dopant dose is between 10-25mL and 15-35mL, respectively. More preferably between 15-20mL and 25-30 mL.

In a preferred embodiment of the present invention, the PeSC comprises: the cathode comprises a substrate, an anode, an electron transport layer, an active layer (perovskite layer), a hole transport layer, a cathode modification layer and a metal electrode layer. Wherein, the substrate uses a glass substrate, and ITO is used as an anode material. The electron transport layer is mesoporous titanium dioxide or mesoporous tin dioxide. The chemical structural general formula of the active layer (perovskite layer) is CH₃NH₃PbI₃. The metal electrode modification layer is molybdenum trioxide. The metal electrode layer is made of silver, gold, aluminum, magnesium and copper.

The present invention is described below by way of examples, which are not exhaustive, as those skilled in the art will appreciate that the examples are illustrative only. The preparation example is a compound synthesis example, the related chemical raw materials and reagents are all sold in the market or synthesized according to the published literature, and the example is the preparation of the battery device PeSC.

Preparation examples

Synthesis of intermediate M3

The structural formula and the synthetic route of the intermediate M3 are shown as the following chart:

the compound of formula M1 is prepared by the process of: in a 250mL two-necked flask, 2.7g (15.0mmol) of phenoxazine, 10.7g (60.0mmol) of 1-bromo-2-fluorobenzene, 8.5g (20.0mmol) of cesium carbonate and 130mL of N, N-dimethylformamide were sequentially added, and the mixture was heated to 150 ℃ with stirring for reaction for 24 hours. After the reaction is completed, cooling the system to room temperature, pouring the system into water, performing suction filtration under reduced pressure, washing filter residues with a large amount of water, and reacting the filter residues with dichloromethane: petroleum ether is 1: 4 (volume ratio) eluent is separated and purified on a silica gel column to obtain 4.6g M1 with the yield of 92.0%. MS (EI) M/z 337.2[ M ]⁺]. Calculated value of elemental analysis C₁₈H₁₂BrNO (%): c63.93, H3.58, N4.14; measured value: c63.68, H3.52, N4.12.

The compound of formula M2 is prepared by the process of: a250 mL two-necked flask was charged with 2.7g (8.0mmol) of M1, 0.2g (0.8mmol) of benzyltriethylammonium chloride, 5.5g (40.0mmol) of potassium carbonate, 0.31g (1.2mmol) of triphenylphosphine, 0.26g (1.2mmol) of palladium acetate, and 100mL of N, N-dimethylformamide in this order, and the reaction system was degassed, purged with nitrogen, stirred, and heated to 150 ℃ for 3 hours. After the reaction is completed, cooling the system to room temperature, pouring the system into water, performing suction filtration under reduced pressure, washing filter residues with a large amount of water, and reacting the filter residues with dichloromethane: petroleum ether is 1: the eluent of 20 vol% was purified on silica gel column to give 1.8g M2 in 89.5% yield. MS (EI) M/z 257.1[ M +]. Calculated value of elemental analysis C₁₈H₁₁NO (%): c84.03, H4.31, N5.44; measured value: c83.90, H4.27, N5.35.

The compound of formula M3 is prepared by the process of: in a 100mL two-necked flask, 1.6g (6.2mmol) of M2 was dissolved in 50mL of dichloromethane, and the mixture was stirred in an ice bath. 1mL (19.2mmol) of liquid bromine was added dropwise from a constant pressure dropping funnel. After the addition, the system was gradually warmed to room temperature and reacted for 6 hours. After the reaction is completedPouring the reaction solution into saturated sodium bisulfite solution, extracting for 3 times by dichloromethane, drying the organic phase by anhydrous sodium sulfate, and removing the solvent by rotary drying to obtain a crude product. The crude product was recrystallized from toluene and ethanol solution to give 2.8g M3 in 92.0% yield. MS (EI) M/z 492.91[ M +]. Calculated value of elemental analysis C₁₈H₈Br₃NO (%): c43.77, H1.63, N2.84; measured value: c43.59, H1.55, N2.79.