CN111704624B - Indolo [3,2,1-kl ] phenoxazine compounds, preparation method and application thereof, and electronic device - Google Patents

Indolo [3,2,1-kl ] phenoxazine compounds, preparation method and application thereof, and electronic device Download PDF

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CN111704624B
CN111704624B CN202010626995.8A CN202010626995A CN111704624B CN 111704624 B CN111704624 B CN 111704624B CN 202010626995 A CN202010626995 A CN 202010626995A CN 111704624 B CN111704624 B CN 111704624B
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廖良生
蒋佐权
朱向东
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Abstract

The invention provides an indolo [3,2,1-kl ] phenoxazine compound, application thereof and an electronic device. The indolo [3,2,1-kl ] phenoxazine compound has excellent film forming property and thermal stability by introducing the rigid structure of the indolo [3,2,1-kl ] phenoxazine, and 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 light emitting layer, an electron blocking layer, a hole blocking layer or an electron transport layer, and can reduce driving voltage, improve efficiency, brightness, 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 industrialized development demand can be met.

Description

Indolo [3,2,1-kl ] phenoxazine compounds, preparation method and application thereof, and electronic device
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 developed rapidly 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, etc. due to their simple synthetic steps and excellent chemical properties. In order to further improve the efficiency of the 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 thereof in preparing organic electroluminescent devices, organic field effect transistors, organic solar cells and perovskite solar cells. The indolo [3,2,1-kl ] phenoxazine compound has simple synthesis and purification steps, matched energy level and high hole mobility, so that the indolo [3,2,1-kl ] phenoxazine compound has high 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):
Figure GDA0004038800740000021
wherein R is 1 、R 2 And R 3 Each independently selected from cyano, or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR 1 Or N;
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO 2 、N(R 2 ) 2 、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 One 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;
R 2 represents 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 site 1 、R 2 And R 3 The groups are independently selected from any one of the following general formulas Ar-1 to Ar-29:
Figure GDA0004038800740000031
Figure GDA0004038800740000041
wherein the wavy line represents a bond to the indolo [3,2,1-kl ] phenoxazine nucleus,
R 1 have the according meaning.
Further, R 1 And R 2 Independently 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:
Figure GDA0004038800740000051
Figure GDA0004038800740000061
Figure GDA0004038800740000071
the present invention also provides a method for producing 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 compound 1 、R 2 And R 3 A 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 taken as a core, and various electron-donating groups are modified on the core for regulation, so that a matched energy level, a high hole mobility and a high thermal stability can be obtained, and the energy conversion efficiency is high. 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):
Figure GDA0004038800740000081
wherein R is 1 、R 2 And R 3 Each independently selected from cyano, or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
z represents CR 1 Or N;
R 1 represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO 2 、N(R 2 ) 2 、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 One 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;
R 2 represents 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.
<R 1 And R 3 >
R 1 ～R 3 Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms.
From R 1 ～R 3 The 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, benzanthracene, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenylPentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimerization indenyl, isotridecyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, 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, oxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazanthronyl, diazapyranyl, tetraazapyryl, naphthyridinyl, pyrazinyl, phenazinyl, phenothiazinyl, fluorescenzyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboron, triphenylphosphoxy, diphenylphosphinyloxy, triphenylsilicon group, tetraphenylsilyl, and the like.
In the present invention, preferably, R 1 ～R 3 Each independently selected from a hydrogen atom, a cyano group or optionallyBy one or more R 1 Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms, or optionally substituted by one or more R 1 One or more substituted aromatic heterocyclic groups having 5 to 30 carbon atoms;
preferably, said R is 1 、R 2 And R 3 Each independently selected from any one of the following general formulae Ar-1 to Ar-29:
Figure GDA0004038800740000111
Figure GDA0004038800740000121
wherein the wavy line represents a bond to the parent nucleus, R 1 Have the meaning defined above.
From R 1 ～R 3 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar 1 ～Ar 6 The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by 1 Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R 1 A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.
(R 1 )
R 1 Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO 2 、N(R 2 )、OR 2 、SR 2 、C(＝O)R 2 、P(＝O)R 2 、Si(R 2 ) 3 Substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon having 6 to 40 carbon atoms, or substituted or unsubstituted aromatic hydrocarbon having 5 to 40 carbon atomsOne or more of the aromatic heterocyclic groups of atoms.
From R 1 The 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 R 1 The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R 1 Alkyl having 1 to 20 carbon atoms represented by one or more of the following R 2 And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group 2 The group can be represented by R 2 C＝CR 2 、C≡C、Si(R 2 ) 3 、C＝O、C＝NR 2 、P(＝O)R 2 、SO、SO 2 、NR 2 O, S or CONR 2 And 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 R 1 The 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, or cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.
From R 1 The alkenyl groups 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 R 1 The alkyl group having 1 to 20 carbon atoms represented may have the same substituent as that shown for the substituent. The substituents may take the same pattern as that of the exemplary substituents.
From R 1 The 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 R 1 The 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 R 1 The alkyl group having 1 to 20 carbon atoms represented may have the same substituent as that shown for the substituent. The substituents may take the same pattern as that of the exemplary substituents.
From R 1 The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the formula are exemplified by the aforementioned aromatic hydrocarbon group represented by Ar 1 ～Ar 6 The 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 R 1 The 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 may be exemplified by R 1 The 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 R 1 Substituents or two adjacent R 2 The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R 2 Substitution; where two or more substituents R 1 May be connected to each other and may form a ring.
Preferably represented by R 1 An aromatic hydrocarbon group having 6 to 40 carbon atoms or an aromatic heterocycle having 5 to 40 carbon atomsExamples of the base include: 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 R 2 And (4) substitution.
(R 2 )
R 2 Represents 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 R 2 The alkyl group having 1 to 20 carbon atoms represented by the formula (I) can be exemplified by the group represented by R 1 The alkyl group having 1 to 20 carbon atoms represented represents the same group as that shown.
From R 2 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 by the formula R 1 The 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 R 2 The 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 groups, and the like.
(Z)
Z represents CR 1 Or N, e.g. N, C-H, C-F, C-Cl, C-Br, C-I, C-CN, C-NO 2 Carbon-phenyl, carbon-biphenyl, and the like.
R 1 Have the meaning as defined above.
In a particularly preferred embodiment of the invention:
r of each bit 1 、R 2 And R 3 Each group is independently selected from the following aromatic or heteroaromatic ring systems: phenoxazinyl, phenothiazinyl, dianilino, trianilino, 9-dimethyl-10-phenyl-9, 10-dihydroacridinyl, 10-phenyl-10 hydro-phenothiazinyl; the aromatic or heteroaromatic ring system may be interrupted by one or more R 1 Substitution;
r at each site 1 The groups are independently selected from: hydrogen, straight chain alkyl having 1 to 5C atoms.
Preferably, the compound is selected from any one of the following general formulae 1-1 to 1-51:
Figure GDA0004038800740000161
Figure GDA0004038800740000171
Figure GDA0004038800740000181
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 present 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 positions 3, 7 and 10]Starting with phenoxazine compounds and then coupling by metal-catalyzed coupling reactions, e.g. Suzuki coupling orIntroduction of R by coupling of Buhward-Hartwald (Hartwig-Buchwald) 1 、R 2 And R 3 A group.
In a preferred embodiment of the present invention, the indolo [3,2,1-kl]The phenoxazine compound is a halogen-functionalized compound, and R 1 、R 2 And R 3 The 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 R 1 、R 2 And R 3 A group. Among these, halogen functionalization is preferably bromination, chlorination, iodination, and particularly bromination.
In particular, in the first preferred embodiment described above, the boronic acid functionalized indolo [3,2,1-kl ] phenoxazine compound (intermediate M3) is prepared first, and preferred preparation steps are exemplified below:
Figure GDA0004038800740000182
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 an intermediate M3, adding an introduced R into the system 1 、R 2 And R 3 Reacting the group boric acid functionalized compound with a certain amount of palladium catalyst such as tetrakis (triphenylphosphine) palladium, 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 to 20, preferably 18; by adjusting the reaction conditions, the yield is 75-95%.
In the second preferred embodiment, preferably, M3 is 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 in the range of 15 to 20, preferably 18; 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 a perovskite solar cell device.
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. MoO 3 (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 transmission layer is mesoporous titanium dioxide or mesoporous tin dioxide. The chemical structural general formula of the active layer (perovskite layer) is CH 3 NH 3 PbI 3 . 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 examples are compound synthesis examples, the related chemical raw materials and reagents are all commercially available or synthesized according to published documents, and the examples are preparation of battery devices PeSC.
Preparation examples
Synthesis of intermediate M3
The structural formula and the synthetic route of the intermediate M3 are shown as follows:
Figure GDA0004038800740000201
the preparation method of the compound of the formula M1 comprises the following steps: in a 250mL two-necked flask, 2.7g (15.0 mmol) of phenoxazine, 10.7g (60.0 mmol) of 1-bromo-2-fluorobenzene, 8.5g (20.0 mmol) 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, carrying out suction filtration under reduced pressure, washing filter residues with a large amount of water, and reacting the filter residues with dichloromethane: petroleum ether =1:4 (volume ratio) eluent on silica gel column separation purification, obtained 4.6g M1, yield 92.0%. M/z 337.2[ MS (EI) ] + ]. Calculated value of elemental analysis C 18 H 12 BrNO (%): c63.93, H3.58, N4.14; measured value: c63.68, H3.52 and N4.12.
The preparation method of the compound of the formula M2 comprises the following steps: a250 mL two-necked flask was charged with 2.7g (8.0 mmol) of M1, 0.2g (0.8 mmol) of benzyltriethylammonium chloride, 5.5g (40.0 mmol) of potassium carbonate, 0.31g (1.2 mmol) of triphenylphosphine, 0.26g (1.2 mmol) 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 =1:20 The eluent (by volume) was separated and purified on a silica gel column to give 1.8g of M2 in 89.5% yield. MS (EI) m/z 257.1[ m + ]]. Calculated value of elemental analysis C 18 H 11 NO (%): c84.03, H4.31, N5.44; measured value: c83.90, H4.27, N5.35.
The preparation method of the compound of the formula M3 comprises the following steps: in a 100mL two-necked flask, 1.6g (6.2 mmol) of M2 was dissolved in 50mL of dichloromethane, and the resulting solution was stirred in an ice bath. 1mL (19.2 mmol) 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 was completed, the reaction solution was poured into a saturated sodium hydrogen sulfite solution, extracted with dichloromethane 3 times, and the organic phase was dried over anhydrous sodium sulfate, followed by spin-drying to remove the solvent to obtain a crude product. The crude product was recrystallized from a solution of toluene and ethanol to give 2.8g of M3 in 92.0% yield. MS (EI) m/z 492.91[ m ] +]. Calculated value of elemental analysis C 18 H 8 Br 3 NO (%): c43.77, H1.63, N2.84; measured value: c43.59, H1.55, N2.79.
Example 1
The structural formulas and synthetic routes of the compounds 1-21 are shown below:
Figure GDA0004038800740000211
a100 mL two-necked flask was charged with 0.5g (1.1 mmol) of M3, 1.4g (4.0 mmol) of 4,4 '-dimethoxy-4' -triphenylamine borate, 1.7g (16.0 mmol) of sodium carbonate, 40mL of toluene, and,6.4mL ethanol, 8mL water. After bubbling the mixture with nitrogen for 30 minutes, 0.06g (0.05 mmol) of tetrakis (triphenylphosphine) palladium catalyst was added, and the mixture was heated and stirred at 106 ℃ overnight. After cooling the reaction to room temperature, the mixture was diluted with water (50 mL) and ethyl acetate (50 mL). The aqueous layer was extracted with 100mL × 3 of ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by rotary drying to obtain the crude product. The use of petroleum ether: ethyl acetate =4:1 (volume ratio) as an eluent solvent on a silica gel column to obtain 1.20g of green solid with a yield of 91%. MS (MALDI-TOF) m/z 1166.4[ 2 ] M +]. Calculated value of elemental analysis C 78 H 62 N 4 O 7 (%): c80.25, H5.35, N4.80; measured value: c80.12, H5.32, N4.76.
Example 2
The structural formulas and synthetic routes of the compounds 1-9 are shown below:
Figure GDA0004038800740000221
a250 mL two-necked flask was charged with 1.1g (2.3 mmol) of M3, 1.9g (8.2 mmol) of 4,4' -dimethoxy-diphenylamine, 0.8g (8.2 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium in this order, and after degassing the reaction system, 150mL of toluene was added under nitrogen protection, and the mixture was stirred and heated to 106 ℃ to react for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out suction filtration under reduced pressure, washing filter residues by using a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and reacting the crude product with petroleum ether: ethyl acetate =3: the eluent of 1 (volume ratio) is separated and purified on a silica gel column to obtain 2.0g of 1-9, and the yield is 92%. MS (MALDI-TOF) m/z 938.3[ m ] +]. Calculated value of elemental analysis C 60 H 36 N 4 O 7 (%): c76.74, H5.37, N5.97; measured value: c76.55, H5.32 and N5.92.
Referring to FIG. 1, FIG. 1 shows the ultraviolet absorption spectra (UV-Vis) and room temperature fluorescence spectra (PL) of products 1-21 and 1-9. Diluted solution of ultraviolet absorption Spectroscopy in methylene chloride (1X 10) -5 mol/L) is measured; fluorescence spectrum in toluene at room temperatureSolution (1X 10) -3 mol/L) was determined.
Example 3
The structural formula and the synthetic route of the compounds 1-5 are shown as follows:
Figure GDA0004038800740000231
a250 mL two-necked flask was charged with 1.1g (2.3 mmol) of M3, 1.6g (8.2 mmol) of 4,4' -dimethyldiphenylamine, 0.8g (8.2 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium in this order, and after degassing the reaction system, 150mL of toluene was added under a nitrogen atmosphere, and the mixture was stirred and heated to 106 ℃ to react for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: ethyl acetate =3: the eluent of 1 (volume ratio) is separated and purified on a silica gel column to obtain 1.7g of 1-5, the yield is 90%. MS (EI) m/z 842.4[ M + ]]. Calculated value of elemental analysis C 60 H 50 N 4 O (%): c85.48, H5.98, N6.65; measured value: c85.41, H5.92, N6.55.
Example 4
The structural formulas and synthetic routes of the compounds 1-17 are shown below:
Figure GDA0004038800740000241
a100 mL two-necked flask was charged with 0.5g (1.1 mmol) of M3, 1.3g (4.0 mmol) of 4- (di-p-methylphenylamino) phenylboronic acid, 1.7g (16.0 mmol) of sodium carbonate, 40mL of toluene, 6.4mL of ethanol, and 8mL of water in this order. After bubbling the mixture with nitrogen for 30 minutes, 0.06g (0.05 mmol) of tetrakis (triphenylphosphine) palladium catalyst was added, and the mixture was stirred at 106 ℃ overnight. After cooling the reaction to room temperature, the mixture was diluted with water (50 mL) and ethyl acetate (50 mL). The aqueous layer was extracted with 100mL of ethyl acetate X3. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by rotary drying to obtain the crude product. The use of petroleum ether: ethyl acetate =4:1 (volume ratio)) Separation and purification on silica gel column as eluent solvent gave 1.06g 1-17 in 90% yield. MS (EI) m/z 1070.50[ M + ]]. Calculated value of elemental analysis C 78 H 62 N 4 O (%): c88.44, H5.83, N5.23; measured value: 88.35, H5.79, N5.19.
Example 5
The structural formula and the synthetic route of the compound 1-2 are shown as follows:
Figure GDA0004038800740000251
a250 mL two-neck flask was charged with 1.1g (2.3 mmol) of M3, 1.5g (8.2 mmol) of phenoxazine, 0.8g (8.2 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium in this order, and after degassing the reaction system, 150mL of toluene was added under nitrogen protection, and the mixture was stirred and heated to 106 ℃ for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: ethyl acetate =3:1 (volume ratio) of eluent is separated and purified on a silica gel column to obtain 1.6g of 1-2, and the yield is 89%. MS (EI) m/z 800.2[ m + ]]. Calculated value of elemental analysis C 54 H 32 N 4 O 4 (%): c80.99, H4.03, N7.00; measured value: c80.85, H3.95 and N6.95.
Example 6
The structural formula and the synthetic route of the compounds 1-3 are shown as follows:
Figure GDA0004038800740000252
a250 mL two-necked flask was charged with 1.1g (2.3 mmol) of M3, 1.6g (8.2 mmol) of phenothiazine, 0.8g (8.2 mmol) of sodium tert-butoxide, 0.1g (0.3 mmol) of tri-tert-butylphosphine tetrafluoroborate, and 0.27g (0.3 mmol) of tris (dibenzylideneacetone) dipalladium in this order, and after degassing the reaction system, 150mL of toluene was added under a nitrogen blanket, and the mixture was stirred and heated to 106 ℃ for 12 hours. After the reaction is completed, theCooling the system to room temperature, carrying out vacuum filtration, washing filter residues with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and reacting the crude product with petroleum ether: ethyl acetate =3:1 (volume ratio) on a silica gel column to obtain 1.8g of 1-3, the yield is 92%. MS (EI) m/z 848.18[ M + ]]. Calculated value of elemental analysis C 54 H 32 N 4 OS 3 (%): c76.39, H3.80, N6.60; measured value: c76.29, H3.75 and N6.51.
Device embodiment
Examples 7 to 12
Preparing a device: the FTO transparent conductive glass substrate is subjected to ultrasonic treatment in a commercial cleaning agent, washed in deionized water, repeatedly washed three times by using the deionized water, acetone and ethanol, baked in a clean environment to completely remove moisture, and treated by using an ultraviolet lamp and ozone to remove residual organic matters. The titanium dioxide is coated on the FTO substrate in a deposition mode, the rotating speed is 1000-4000rmp, the time is 10-40s, then the annealing is carried out for 60-100min at 120-180 ℃, and the step is repeated to ensure that the thickness of the electron transmission layer is 60-160nm. Placing the titanium dioxide in a glove box, spin-coating an active layer on the titanium dioxide at 2000-5000rmp, annealing at 60-120 deg.C in an atmosphere with atmospheric humidity of 5-30% and thickness of 150-350nm. Dissolving a hole transport material in chlorobenzene at a concentration of 20-100mg/mL, adding 10-25mL of lithium bistrifluoromethanesulfonylimide (Li-TFSI) and 15-35mL of a tetra-tert-butylpyridine (TBP) solution to the hole transport material solution to improve film-forming properties and lower HOMO energy level, and then spin-coating the hole transport material solution onto the active layer at a thickness of 80-250nm. Finally, vacuum evaporating molybdenum trioxide with the thickness of 10-20nm on the hole transport layer, and then evaporating a silver electrode with the thickness of 60-180 nm.
Testing the performance of the device: the current-voltage characteristics of the devices were determined by Keithley Source measurement system (2400Series Source Meter, keithley Instruments) with calibration, all at a normalized Air (AM) 1.5sunlight at 100mW cm -2 (Newport, class AAA solar simulator, 94023A-U).
The examples relate to compounds having the following structure:
Figure GDA0004038800740000271
the structures of examples 7-12 (devices PeSC 1-6, respectively) and the film thicknesses of the respective layers were as follows:
PeSC 1:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-21(150nm)/MoO 3 (10nm)/Ag(100nm)
PeSC 2:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-9(150nm)/MoO 3 (10nm)/Ag(100nm)
PeSC 3:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-5(150nm)/MoO 3 (10nm)/Ag(100nm)
PeSC 4:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-17(150nm)/MoO 3 (10nm)/Ag(100nm)
PeSC 5:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-2(150nm)/MoO 3 (10nm)/Ag(100nm)
PeSC 6:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/1-3(150nm)/MoO 3 (10nm)/Ag(100nm)
comparative example
The preparation method of comparative example 1 is the same as that of the example, only the hole transport material is changed, and the device structure of comparative example 1 is as follows:
PeSC 7:
FTO(150nm)/TiO 2 (100nm)/CH 3 NH 3 PbI 3 (250nm)/spiro-OMeTAD(150nm)/MoO 3 (10nm)/Ag(100nm)
the device performance data is shown in table 1:
table 1: device performance data
Figure GDA0004038800740000281
It can be seen from the above table that devices using the compounds of the present invention can achieve comparable device efficiencies compared to the commercial spiro-OMeTAD hole transport materials commonly used in the industry, some of which are even over 20% more efficient. From the viewpoint of the steps of synthetic purification of materials, the steps of synthesis and purification of the compound of the present invention are relatively simple.
In conclusion, the indolo [3,2,1-kl ] phenoxazine compound provided by the invention has excellent film forming property and thermal stability by introducing an indolo [3,2,1-kl ] phenoxazine rigid structure, and 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 can effectively separate donor groups from acceptor groups, so that the indolo [3,2,1-kl ] phenoxazine compound is an ideal framework for constructing a thermal activation delayed fluorescence material. The preparation method of the indolo [3,2,1-kl ] phenoxazine compound is simple, raw materials are easy to obtain, and the industrialized development demand can be met.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (4)

1. An indolo [3,2,1-kl ] phenoxazine compound, characterized by being selected from any one of the following general formulas:
Figure FDA0003993898900000011
2. 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 hole transport layer interposed between the first electrode and the second electrode, the hole transport layer comprising the indolo [3,2,1-kl ] phenoxazine compound according to claim 1.
3. Use of an indolo [3,2,1-kl ] phenoxazine compound according to claim 1 as a light emitting material, electron transporting material, electron blocking material, hole injecting material or hole blocking material in an electronic device which is a perovskite solar cell.
4. Use of an indolo [3,2,1-kl ] phenoxazine compound according to claim 1 in the preparation of a hole transport layer.
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JP5782836B2 (en) * 2011-05-27 2015-09-24 コニカミノルタ株式会社 ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE, LIGHTING DEVICE, AND COMPOUND
US10336772B2 (en) * 2015-12-28 2019-07-02 Samsung Electronics Co., Ltd. Bicarbazole compound, material for organic light-emitting device including bicarbazole compound, and organic light-emitting device including bicarbazole compound
KR101939287B1 (en) * 2016-05-10 2019-01-16 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising the same
KR102656921B1 (en) * 2016-12-20 2024-04-16 솔루스첨단소재 주식회사 Organic compounds and organic electro luminescence device comprising the same
CN110256447A (en) * 2019-07-09 2019-09-20 苏州大学 Indoles simultaneously [3,2,1-jk] carbazole derivates, preparation method and application and electronic device

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