CN110256447A - Indoles simultaneously [3,2,1-jk] carbazole derivates, preparation method and application and electronic device - Google Patents
Indoles simultaneously [3,2,1-jk] carbazole derivates, preparation method and application and electronic device Download PDFInfo
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Abstract
The present invention relates to a kind of indoles simultaneously [3,2,1-jk] carbazole derivates, preparation method and application and electronic device, the hole mobility of the indoles simultaneously [3,2,1-jk] carbazole derivates is up to 6.5 × 10‑4cm2V‑1S‑1, can be used as hole mobile material and apply in solar cell device, can effectively inhibit the consume of energy, improve the performances such as energy conversion efficiency, device lifetime, current density, fill factor and the cut-in voltage of solar cell device.
Description
Technical field
The present invention relates to a kind of indoles simultaneously [3,2,1-jk] carbazole derivates, preparation method and application and electronics devices
Part belongs to organic photoelectrical material technical field.
Background technique
Since two thousand nine, perovskite solar battery (PeSC) due to its width strong absorption band, length exciton diffusion away from
It is concerned and develops swift and violent from, higher photoelectric conversion efficiency.The perovskite battery device prepared currently based on solwution method
Energy conversion efficiency broken through 23% and in atmospheric environment the time of steady operation already exceed 1000 hours, these
As a result the great potential of perovskite solar battery is sufficiently shown.
The structure of perovskite battery mainly includes active layer (calcium titanium ore bed), hole transmission layer and electron transfer layer.Hole
Transport layer plays the role of that hole is extracted and transmitted and inhibits Carrier recombination.One hole transmission layer needs haveing excellent performance
With suitable energy level, higher cavity transmission ability and preferable thermal stability.Commonly organic hole transport material includes
Spirofluorene derivative, pyrene analog derivative, conducting polymer.However these common hole mobile materials usually have it is more complex
Synthesis and purification step cost with higher are to increase commercial cost.Currently, simultaneously [3,2,1-jk] carbazole is derivative for indoles
Object is due to its simple synthesis step, excellent chemical property, in Organic Light Emitting Diode, dye-sensitized solar cells
Equal fields are reported.In order to further improve efficiency and the reduction of perovskite solar battery from the angle of hole mobile material
The cost of battery, with indoles, simultaneously this chemical structure of [3,2,1-jk] carbazole is core for we, by introducing electron donating group modification,
A series of indoles that can be used as hole mobile material simultaneously [3,2,1-jk] carbazole derivates are obtained.
Summary of the invention
The purpose of the present invention is to provide a series of new can be used as the indoles of hole mobile material simultaneously [3,2,1-jk] click
Zole derivatives, and its preparing the application in perovskite solar battery.Such indoles simultaneously [3,2,1-jk] carbazole derivates by
In the synthesis and purification step with simplicity, and because there is matched energy level, higher hole mobility, to apply
Energy conversion efficiency with higher in perovskite solar battery.
In order to achieve the above objectives, the invention provides the following technical scheme: a kind of indoles simultaneously [3,2,1-jk] carbazole derivates,
For the compound indicated comprising following general formula (1):
Wherein, the indoles simultaneously simultaneously [3,2,1-jk] the carbazole parent nucleus connection 3 of the indoles in [3,2,1-jk] carbazole derivates
A R group, any one of aryl/heteroaromatic rings that the R group in each site is 6~30 independently selected from annular atom number；
The annular atom number be 6~30 aryl/heteroaromatic rings in, the hydrogen-based being connect with carbon atoms on a benzene ring by one or
Multiple R1Group replaces；The R in each site1Group is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted carbon atom number
For 1~40 straight chained alkyl/alkoxy/thioalkyl groups, alternatively, the branch that substituted or unsubstituted carbon atom number is 3~40
Any one of chain or cricoid alkyl/alkoxy/thioalkyl groups.
Further, in the heteroaromatic rings that the annular atom number is 6~30, the hetero atom in each site independently selected from N,
Any one of O or S.
Further, the R group in each site is independently selected from any one of following general formula Ar-1 to Ar-11:
Wherein, the R in each site1Group is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted carbon atom number
1~40 straight chained alkyl/alkoxy/thioalkyl groups, alternatively, the branch that substituted or unsubstituted carbon atom number is 3~40
Or any one of cricoid alkyl/alkoxy/thioalkyl groups.
Further, the R group is selected from by the R1The substituted or unsubstituted pyridyl group of group, acridinyl, 9,9- bis-
Methyl-1 0- phenyl-acridan base, phenoxazine base, -10 hydrogen of 10- phenyl-phenoxazine base, phenothiazinyl, 10- phenyl -
10 hydrogen-phenothiazinyl, hexichol amido, triphenylamine base, dibenzofuran group, dibenzothiophene, dibenzothiophenes sulfuryl, hexichol
Base triazine radical, meta-terphenyl base, diphenylpyrimidin base, two phenenyl phosphinyl, dimethylaminoborane base, tri-phenyl-silane base, triphen
Any one of methylmethane base, xenyl or naphthalene, the R in each site1Group independently is hydrogen or carbon atom number is 1~4
Straight chained alkyl.
Further, the R group in each site is independently selected from by the R1The substituted or unsubstituted phenoxazine of group
Base, phenothiazinyl, hexichol amido, triphenylamine base, 9,9- dimethyl -10- phenyl-acridan base, 10- phenyl -10
Any one of hydrogen-phenothiazinyl, the R in each site1The straight chained alkyl that group independently is hydrogen or carbon atom number is 1~4.
Further, the compound is selected from any one of following formula 1-1 to 1-33:
The present invention also provides a kind of preparation methods of indoles according to item simultaneously [3,2,1-jk] carbazole derivates, including
Following steps:
By the indoles of 2,5 and 11 position functionals, simultaneously [3,2,1-jk] carbazole carries out metal catalyzed coupling reaction introducing three
The R group.
Further, the electronic device is selected from organic electroluminescence device, organic field effect tube or perovskite too
Positive energy battery.
The present invention also provides a kind of electronic devices, have the indoles simultaneously [3,2,1-jk] carbazole derivates.
Further, the electronic device is perovskite solar cell device, the perovskite solar cell device
Including electron transfer layer, perovskite active layer and hole transmission layer, there is the Yin in the perovskite solar cell device
Diindyl simultaneously [3,2,1-jk] carbazole derivates.
Compared with prior art, the beneficial effects of the present invention are: the present invention with indoles simultaneously [3,2,1-jk] carbazole for core,
It is adjusted by modifying all kinds of electron donating groups on it, can get more matched energy level, higher hole mobility and higher
Thermal stability, thus energy conversion efficiency with higher.With commercialized spirobifluorene derivative material spiro-OMeTAD
Compared to having the energy conversion efficiency to compare favourably, wherein being no lack of the device efficiency more than spiro-OMeTAD.And with spiro-
OMeTAD is compared, due to greatly reducing production cost with relatively simple synthesis and purification step, to reduce calcium titanium
The cost of mine solar battery.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the ultra-violet absorption spectrum (UV-Vis) of compound 1-21 and 1-9 and room in the embodiment of the present invention 1 and example 2
Warm fluorescence spectrum (PL)；
Fig. 2 be the embodiment of the present invention 1, in example 2 and comparative example 1 perovskite solar cell device current density and electricity
The curved line relation of pressure.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
The present invention provides a kind of indoles simultaneously [3,2,1-jk] carbazole derivates, for the change indicated comprising following general formula (1)
Close object:
Wherein, the indoles simultaneously simultaneously [3,2,1-jk] the carbazole parent nucleus connection 3 of the indoles in [3,2,1-jk] carbazole derivates
A R group, any one of aryl/heteroaromatic rings that the R group in each site is 6~30 independently selected from annular atom number；
The annular atom number be 6~30 aryl/heteroaromatic rings in, the hydrogen-based being connect with carbon atoms on a benzene ring by one or
Multiple R1Group replaces.The R in each site1Group is independently selected from hydrogen, deuterium, halogen, cyano, the straight chain alkane that carbon atom number is 1~40
Base/alkoxy/thioalkyl groups, the branch or cricoid alkyl/alkoxy/thioalkyl groups that carbon atom number is 3~40；
The straight chained alkyl that the carbon atom number is 1~40 is optionally substituted by halogen or unsubstituted, the branched alkyl that the carbon atom number is 3~40
It is optionally substituted by halogen or unsubstituted.
3 R groups are specifically connected to indoles simultaneously [3,2,1-jk] carbazole parent nucleus 2,5 and 11, and this connection type can
To increase the electron donation of entire molecule, to propose high molecular highest occupied molecular orbital energy level and hole mobility.
Aromatics ring system in the sense of the present invention contains 6 to 30 C atoms, preferably 6 to 18 C atoms in the ring system.This
Heteroaromatic rings in invention meaning are tied up to containing 5 to 30 in the ring system, preferably 6 to 18 C atoms and hetero atom, the hetero atom
It is preferably chosen from N, O and/or S.In the present invention, the number of heteroatoms of compound can be 1-5 (round numbers).Present invention meaning
Aromatics or heteroaromatic ring system in justice is intended to be considered to refer to following system, which not necessarily must only contain aryl or heteroaryl
Base group, but plurality of aryl or heteroaryl group can also be by non-aromatic unit (preferably smaller than the 10% of non-hydrogen atom)
Interruption, which is, for example, C, N, O atom.For example, with two or more aryl groups for example by straight chain or ring-type
Alkyl group or the same by the intermittent system of silyl-group, 9,9 '-spiral shell, two fluorenes, 9,9- diaryl fluorene, triarylamine,
It is considered as aromatics ring system in the sense of the present invention that the system of diaryl ether etc., which is also intended to,.In addition, two of them or more
The system of the mutual Direct Bonding of aryl or heteroaryl group, such as biphenyl, terphenyl or quaterphenyl are equally directed to be considered as virtue
Race or heteroaromatic ring system.
One or more the constituted systems of aromatics or heteroaromatic ring system for example by being derived from following group: benzene, naphthalene,
Anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, fluoranthene, benzofluoranthrene, aphthacene, pentacene, BaP, biphenyl, even benzene, three
Benzene, quaterphenyl, quinquephenyl, trimeric benzene, fluorenes, spiro fluorene, dihydro phenanthrene, dihydropyrene, tetrahydro pyrene, cis or trans indenofluorene, it is cis- or
Trans- list benzo indenofluorene, cis or trans dibenzo indenofluorene, three polyindenes, different three polyindene, three polyindene of spiral shell, different three polyindene of spiral shell,
Furans, benzofuran, isobenzofuran, dibenzofurans, thiophene, benzothiophene, isothiophene, dibenzothiophenes, pyrroles,
Indoles, iso-indoles, indolocarbazole, indeno carbazole, pyridine, quinoline, isoquinolin, acridine, phenanthridines, benzo -5,6- quinoline, benzene
And -6,7- quinoline, benzo -7,8- quinoline, 9,9- dimethyl -10- phenyl-acridan base, -10 hydrogen of 10- phenyl-pheno
Oxazines base, phenthazine, phenoxazine, pyrazoles, indazole, imidazoles, benzimidazole, naphtho- imidazoles, phenanthro- imidazoles, pyridine-imidazole, pyrrole
Piperazine and imidazoles, quinoxaline and imidazoles, oxazole, benzoxazoles, aphthoxazoles, anthra oxazole, phenanthro- oxazole, isoxazole, 1,2- thiophene
Azoles, 1,3- thiazole, benzothiazole, pyridazine, benzo pyridazine, pyrimidine, benzo pyrimidine, quinoxaline, 1,5- naphthodiazine, 2,7- phenodiazine
Miscellaneous pyrene, 2,3- diaza pyrene, 1,6- diaza pyrene, 1,8- diaza pyrene, 4,5- diaza pyrene, tetra- azepine of 4,5,9,10-, pyrrole
Piperazine, azophenlyene, fluorubin, naphthyridines, benzo carboline, phenanthroline, 1,2,3- triazole, 1,2,4- triazole, benzotriazole, 1,2,3- dislike two
Azoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiophene
Diazole, 1,3,4- thiadiazoles, tetrazolium, 1,2,4,5- tetrazine, 1,2,3,4- tetrazine, 1,2,3,5- tetrazine, purine, pteridine, indolizine,
Diazosulfide, diphenylamines, dibenzothiophene, diphenyl triazine radical, meta-terphenyl, diphenylpyrimidin, diphenyl phosphine oxide, two
Methylboranyl, tri-phenyl-silane, triphenyl methane etc., above-mentioned group can be substituted or unsubstituted.
Preferably, the R group is selected from any one of following general formula Ar-1 to Ar-11:
Wherein, the R in each site1Group is independently selected from hydrogen, deuterium, halogen, cyano, the straight chain alkane that carbon atom number is 1~40
Base/alkoxy/thioalkyl groups, the branch or cricoid alkyl/alkoxy/thioalkyl groups that carbon atom number is 3~40；
The straight chained alkyl that the carbon atom number is 1~40 is optionally substituted by halogen or unsubstituted, the branched alkyl that the carbon atom number is 3~40
It is optionally substituted by halogen or unsubstituted.Preferably, the R in each site1Group is independently selected from hydrogen, deuterium, fluorine, cyano；With 1 to 10 C
The straight chained alkyl of atom, alkoxy or branch or cricoid alkyl or alkoxy with 3 to 10 C atoms, the straight chain
Alkyl or branched alkyl are optionally replaced by fluorine.It is highly preferred that the R in each site1Group is independently selected from hydrogen, fluorine；With 1
To straight chained alkyl such as methyl, ethyl, propyl, the butyl of 5 C atoms, branch or cricoid alkyl with 3 to 6 C atoms.
In a kind of particularly preferred embodiment of the invention:
Everybody R group is independently selected from following aromatics or heteroaromatic ring system: phenoxazine base, phenothiazinyl, diphenylamines
Base, triphenylamine base, 9,9- dimethyl -10- phenyl-acridan base, in -10 hydrogen of 10- phenyl-phenothiazinyl；The virtue
Race or heteroaromatic ring system can be by one or more R1Replace；
The R in each site1Group is independently selected from hydrogen, the straight chained alkyl with 1 to 5 C atom.
Preferably, the compound is selected from any one of following formula 1-1 to 1-33:
The preparation method of the indoles that the present invention also provides a kind of according to simultaneously [3,2,1-jk] carbazole derivates, including with
Lower step:
Synthesis step known to persons of ordinary skill in the art, such as the coupling of bromination, Suzuki (Suzuki), Bu He can be passed through
Grindelwald-Hartwig (Hartwig-Buchwald) coupling etc., to prepare compound according to the present invention.
Usually from the indoles of 2,5 and 11 position functionals, simultaneously [3,2,1-jk] carbazole derivates are opened for the compound of the present invention synthesis
Begin, then passes through metal catalyzed coupling reaction such as Suzuki (Suzuki) coupling or Buchwald-Hartwig (Hartwig-
Buchwald it) is coupled and introduces 3 R groups.
In the preferred embodiment of the present invention, the three carbazole Spirocyclic derivatives of phenyl are halogen-functionalized changes
Object is closed, and R group is originated from the functionalized compound of boronic acid derivatives.
In second of preferred embodiment of the invention, simultaneously [3,2,1-jk] carbazole derivates are halogen officials to the indoles
The compound of energyization reacts with the compound of amine derivant under the action of palladium class catalyst and introduces R group.Wherein, halogen
Element is functionalized preferred bromination, chlorination, iodate, especially bromination.
Specifically, the first as described above preferred embodiment, need to first prepare the functionalized indoles of boric acid simultaneously [3,2,
1-jk] carbazole derivates (intermediate M3), preferred preparation step example is as follows:
By controlling reaction condition, the yield of M1 can reach 80-95%, and the yield of M2 can reach 70-95%, the yield of M3
60-95% can be arrived.After obtaining intermediate M3, the boric acid functionalized compounds that can introduce R group are added in system, and certain
Palladium class catalyst such as tetrakis triphenylphosphine palladium, Anhydrous potassium carbonate, the toluene of amount, second alcohol and water is under nitrogen protection at 80-120 DEG C
Reaction 20-35 hours, end of reaction.Solvent is boiled off, with methylene chloride and water dissolution residual substance, washing separates organic layer, water layer
It is extracted with dichloromethane, merges organic layer, be washed with water twice to neutrality, after boiling off solvent, column chromatography for separation is dried to obtain production
Object.The molar ratio of intermediate M3 and tetrakis triphenylphosphine palladium is in 15-20:1, preferably 18:1；By adjusting reaction condition, yield exists
75-95%.
Second of preferred embodiment as described above, it is anti-preferably by M3 and the functionalized compound of amine derivant
It answers, tris(dibenzylideneacetone) dipalladium, sodium tert-butoxide, tetrafluoro boric acid tri-tert-butylphosphine, toluene is added in system, protected in argon gas
It is reacted 10-30 hours at shield is 90-120 DEG C lower, end of reaction.It filters, decompression boils off solvent, and column chromatography for separation is dried to obtain production
Object.The molar ratio of intermediate M3 and tris(dibenzylideneacetone) dipalladium is in 15-20:1, preferably 18:1；By adjusting reaction condition,
Yield is up to 78-95%.
The present invention also provides according to the indoles simultaneously [3,2,1-jk] carbazole derivates in being used to prepare electronic device
Application, the electronic device be selected from organic electroluminescence device, organic field effect tube or perovskite solar battery, especially
It is the application in the hole mobile material being used to prepare in perovskite solar cell device.
The present invention additionally relates to the electronic device comprising at least one the compounds of this invention.The electronic device is preferably
It is brilliant selected from perovskite solar battery (PeSC), organic electroluminescence device (Organic Light Emitting Diode, OLED), organic effect
Body pipe (O-FET), organic solar batteries (O-SC), Organic Thin Film Transistors (O-TFT), organic light-emitting transistor (O-LET),
Organic integrated circuits (O-IC), organic dye sensitized solar battery (ODSSC), organic optical detector, organophotoreceptorswith,
Organic field quenching device (O-FQD), light-emitting electrochemical cell (LEC), organic laser diode (O-laser) and organic plasma
Body ballistic device etc., preferably organic electroluminescence device (OLED).
One PeSC is generally comprised: substrate, such as (but not limited to) glass, plastics, metal；Anode, such as Fluorin doped
Tin oxide (FTO) anode；Electron transfer layer；Perovskite active layer；Hole transmission layer；Cathodic modification layer, such as MoO3；Yin
Pole, such as Ag.It is noted, however, that intermediate every layer can have one or more layers and every layer to be not necessarily present.
The compound of the present invention can be used for the device it is any one or more layers, but be preferred for hole transmission layer, because
It is it with high hole mobility, suitable energy level and stability are good.
Hole transmission layer dopant of the invention is not particularly limited, preferably double trifluoromethanesulfonimide lithium (Li-
) and tetra-tert pyridine (TBP) TFSI.In order to improve device efficiency, dopant dose is respectively between 10-25mL and 15-35mL.
Between further preferred 15-20mL and 25-30mL.
In a preferred embodiment of the invention, PeSC includes: substrate, anode, electron transfer layer, active layer (perovskite
Layer), hole transmission layer, cathodic modification layer, metal electrode layer.Wherein, substrate uses glass substrate, and ITO makees anode material.It is described
Electron transfer layer be mesoporous TiO 2 or meso-porous titanium dioxide stannic oxide.Described active layer (calcium titanium ore bed) chemical structure
General formula is CH3NH3PbI3.The metal electrode decorative layer is molybdenum trioxide.The metal electrode layer material be silver, gold,
Aluminium, magnesium, copper.
Embodiment is exemplified below to illustrate the present invention, it will be appreciated by those skilled in the art that the example is merely exemplary
Illustrate, and the explanation of non-exclusive.Preparation example is compound synthesis example, related chemical raw material and reagent be it is commercially available or by
Open source literature synthesis, embodiment are the preparation of battery device PeSC.
Prepare embodiment
The synthesis of intermediate M3
The structural formula and synthetic route of intermediate M3 is as shown below:
Formula M1 compound the preparation method comprises the following steps: sequentially added in 250mL two mouth flask 2.5g (15.0mmol) carbazole,
The bromo- 2- fluorobenzene of 10.7g (60.0mmol) 1-, 8.5g (20.0mmol) cesium carbonate and 130mL n,N-Dimethylformamide, stirring
150 DEG C are heated to react 24 hours.After fully reacting, system is cooled to room temperature, is poured into water, decompression filters, and with largely
Filter residue is washed, by filter residue methylene chloride: the eluant, eluent of petroleum ether=1:4 (volume ratio) carries out separating-purifying on a silica gel column,
Obtain 4.4g M1, yield 92.0%.MS(EI):m/z 321.2[M+].Elemental analysis calculated value C18H12BrN (%): C
67.10, H 3.75, N 4.35；Measured value: C 66.98, H 3.72, N 4.32.
Formula M2 compound the preparation method comprises the following steps: sequentially adding 2.87g (8.0mmol) M1,0.2g in 250mL two mouth flask
(0.8mmol) benzyltriethylammoinium chloride, 5.5g (40.0mmol) potassium carbonate, triphenylphosphine, 0.26g (1.2mmol) palladium acetate,
100mL n,N-Dimethylformamide will use nitrogen protection after reaction system degasification, be heated with stirring to 150 DEG C and react 3 hours.Instead
Should completely after, system is cooled to room temperature, is poured into water, decompression filters, and with massive laundering filter residue, by filter residue dichloromethane
Alkane: the eluant, eluent of petroleum ether=1:20 (volume ratio) carries out separating-purifying on a silica gel column, obtains 1.7g M2, yield 89.5%.
MS(EI):m/z 241.11[M+].Elemental analysis calculated value C18H11N (%): C 89.60, H 4.60, N 5.80；Measured value: C
89.50, H 4.56, N 5.75.
Formula M3 compound the preparation method comprises the following steps: in 100mL two mouth flask, 1.5g (6.2mmol) M2 is dissolved in 50mL bis-
Chloromethanes is placed in ice bath and stirs.1mL (19.2mmol) bromine is added dropwise with constant pressure funnel.It finishes, gradually system heats up
To room temperature, react 6 hours.After fully reacting, reaction solution is poured into saturation solution of sodium bisulfite, is extracted with dichloromethane 3
It is secondary, after organic phase anhydrous sodium sulfate drying, it is spin-dried for removing solvent and obtains crude product.Crude product carries out in toluene and ethanol solution
Recrystallization, obtains 2.7g M3, yield 92.0%.MS(EI):m/z 476.91[M+].Elemental analysis calculated value C18H8Br3N
(%): C 45.23, H 1.69, N 2.93；Measured value: C 44.99, H 1.65, N 2.89.
Embodiment 1
The structural formula and synthetic route of compound 1-21 is as shown below:
0.5g (1.1mmol) M3,1.4g (4.0mmol) 4,4'- dimethoxy-is sequentially added in 100mL two mouth flask
4 "-boric acid triphenylamines, 1.7g (16.0mmol) sodium carbonate, 40mL toluene, 6.4mL ethyl alcohol, 8mL water.By mixture nitrogen drum
0.06g (0.05mmol) tetrakis triphenylphosphine palladium catalyst is added after 30 minutes in bubble, and heating stirring is stayed overnight at 106 DEG C.It will be anti-
After should being cooled to room temperature, mixture water (50mL) and ethyl acetate (50mL) dilution.It is extracted again with ethyl acetate 100mL × 3
Water layer.After organic phase anhydrous sodium sulfate drying, it is spin-dried for removing solvent and obtains crude product.Use petroleum ether: ethyl acetate=4:1
(volume ratio) carries out separating-purifying as eluant, eluent solvent on a silica gel column, obtains 1.20g green solid, yield 91%.MS
(MALDI-TOF):m/z 1150.4[M+].Elemental analysis calculated value C78H62N4O6(%): C 81.37, H 5.43, N 4.87；
Measured value: C 81.32, H 5.42, N 4.86.
Embodiment 2
The structural formula and synthetic route of compound 1-9 is as shown below:
1.1g (2.3mmol) M3,1.9g (8.2mmol) 4,4'- dimethoxy-is sequentially added in 250mL two mouth flask
Diphenylamines, 0.8g (8.2mmol) sodium tert-butoxide, 0.1g (0.3mmol) tetrafluoro boric acid tri-tert-butylphosphine, 0.27g (0.3mmol) three
(dibenzalacetone) two palladium under nitrogen protection, will be added 150mL toluene, be heated with stirring to 106 DEG C after reaction system degasification
Reaction 12 hours.After fully reacting, system is cooled to room temperature, decompression filters, and washs filter residue with a large amount of methylene chloride, will filter
Liquid is concentrated to get crude product, crude product petroleum ether: the eluant, eluent of ethyl acetate=3:1 (volume ratio) is divided on a silica gel column
From purification, 1.9g 1-9, yield 92% are obtained.MS(MALDI-TOF):m/z 922.3[M+].Elemental analysis calculated value
C60H36N4(%): C 88.64, H 4.46, N 6.07；Measured value: C 88.55, H 4.42, N 6.03.
Referring to Figure 1, Fig. 1 is the ultra-violet absorption spectrum (UV-Vis) and Room temperature PL spectrum of product 1-21 and 1-9
(PL).Weak solution (1 × 10 of the ultra-violet absorption spectrum in methylene chloride-5Mol/L it is measured in)；Room temperature PL spectrum is in toluene solution
(1×10-3Mol/L it is measured in).
Embodiment 3
The structural formula and synthetic route of compound 1-5 is as shown below:
1.1g (2.3mmol) M3,1.6g (8.2mmol) 4,4'- dimethyl hexichol is sequentially added in 250mL two mouth flask
Amine, 0.8g (8.2mmol) sodium tert-butoxide, 0.1g (0.3mmol) tetrafluoro boric acid tri-tert-butylphosphine, 0.27g (0.3mmol) three (two
BENZYLIDENE ACETONE) two palladiums, 150mL toluene will be added after reaction system degasification under nitrogen protection, and be heated with stirring to 106 DEG C instead
It answers 12 hours.After fully reacting, system is cooled to room temperature, decompression filters, and washs filter residue with a large amount of methylene chloride, by filtrate
Be concentrated to get crude product, crude product petroleum ether: the eluant, eluent of ethyl acetate=3:1 (volume ratio) is separated on a silica gel column
Purification, obtains 1.7g 1-5, yield 90%.MS(EI):m/z 826.40[M+].Elemental analysis calculated value C60H36N4(%): C
87.13, H 6.09, N 6.77；Measured value: C 87.01, H 6.07, N 6.75.
Embodiment 4
The structural formula and synthetic route of compound 1-17 is as shown below:
0.5g (1.1mmol) M3,1.3g (4.0mmol) 4- (two p-methylphenyls are sequentially added in 100mL two mouth flask
Amido) phenyl boric acid, 1.7g (16.0mmol) sodium carbonate, 40mL toluene, 6.4mL ethyl alcohol, 8mL water.Mixture is bubbled with nitrogen
After 30 minutes, 0.06g (0.05mmol) tetrakis triphenylphosphine palladium catalyst is added, heating stirring is stayed overnight at 106 DEG C.It will reaction
After being cooled to room temperature, mixture water (50mL) and ethyl acetate (50mL) dilution.The extraction water of ethyl acetate 100mL × 3 is used again
Layer.After organic phase anhydrous sodium sulfate drying, it is spin-dried for removing solvent and obtains crude product.Use petroleum ether: ethyl acetate=4:1 (body
Product ratio) it is used as eluant, eluent solvent to carry out separating-purifying on a silica gel column, obtain 1.04g 1-17, yield 90%.MS(EI):m/
z 1054.50[M+].Elemental analysis calculated value C78H62N4(%): C 88.77, H 5.92, N 5.31；Measured value: 88.65, H
5.89, N 5.29.
Embodiment 5
The structural formula and synthetic route of compound 1-2 is as shown below:
1.1g (2.3mmol) M3,1.5g (8.2mmol) phenoxazine, 0.8g are sequentially added in 250mL two mouth flask
(8.2mmol) sodium tert-butoxide, 0.1g (0.3mmol) tetrafluoro boric acid tri-tert-butylphosphine, three (dibenzylidene third of 0.27g (0.3mmol)
Ketone) two palladiums, after reaction system degasification under nitrogen protection, 150mL toluene will be added, it is 12 small to be heated with stirring to 106 DEG C of reactions
When.After fully reacting, system is cooled to room temperature, decompression filters, and washs filter residue with a large amount of methylene chloride, and filtrate is concentrated to give
To crude product, crude product petroleum ether: the eluant, eluent of ethyl acetate=3:1 (volume ratio) carries out separating-purifying on a silica gel column,
Obtain 1.6g 1-2, yield 89%.MS(EI):m/z 784.25[M+].Elemental analysis calculated value C54H32N4O3(%): C
82.64, H 4.11, N 7.14；Measured value: C 82.55, H 4.08, N 7.10.
Embodiment 6
The structural formula and synthetic route of compound 1-3 is as shown below:
1.1g (2.3mmol) M3,1.6g (8.2mmol) phenthazine, 0.8g are sequentially added in 250mL two mouth flask
(8.2mmol) sodium tert-butoxide, 0.1g (0.3mmol) tetrafluoro boric acid tri-tert-butylphosphine, three (dibenzylidene third of 0.27g (0.3mmol)
Ketone) two palladiums, after reaction system degasification under nitrogen protection, 150mL toluene will be added, it is 12 small to be heated with stirring to 106 DEG C of reactions
When.After fully reacting, system is cooled to room temperature, decompression filters, and washs filter residue with a large amount of methylene chloride, and filtrate is concentrated to give
To crude product, crude product petroleum ether: the eluant, eluent of ethyl acetate=3:1 (volume ratio) carries out separating-purifying on a silica gel column,
Obtain 1.8g 1-3, yield 92%.MS(EI):m/z 832.18[M+].Elemental analysis calculated value C54H32N4S3(%): C
77.86, H 3.87, N 6.73；Measured value: C 77.79, H 3.85, N 6.71.
Device embodiments
Embodiment 7-12
Device preparation: FTO transparent conducting glass substrate is ultrasonically treated in commercial detergent, is rushed in deionized water
Wash, cleaned repeatedly three times with deionized water, acetone, ethyl alcohol, baking completely removes moisture under a clean environment, with ultraviolet lamp and
Ozone treatment FTO electro-conductive glass is to remove remaining organic matter.Titanium dioxide is covered in a manner of depositing on FTO substrate, is turned
Speed is 1000-4000rmp, time 10-40s, and then anneal at 120-180 DEG C 60-100min, and repeating this step makes electronics
Transport layer with a thickness of 60-160nm.It is placed in glove box, one layer of active layer of spin coating, revolving speed are on titanium dioxide
2000-5000rmp, in 60-120 DEG C of the environment annealing that atmospheric humidity is 5-30%, with a thickness of 150-350nm.By hole transport
Material is dissolved in chlorobenzene, concentration 20-100mg/mL, by double trifluoromethanesulfonimide lithiums (Li-TFSI) of 10-25mL and
Tetra-tert pyridine (TBP) solution of 15-35mL is added in hole mobile material solution to improve film forming and reduce HOMO energy
Hole mobile material solution, is then spun on active layer, with a thickness of 80-250nm by grade.Finally hole transmission layer it
On, then 60-180nm silver electrode is deposited in first vacuum evaporation 10-20nm molybdenum trioxide.
Device performance test: the I-E characteristic of device is by with the corrected source Keithley measurement system
(2400Series Source Meter, Keithley Instruments) is completed, in simulated when test
airmass(AM)1.5sunlight at 100mW cm-2(Newport,Class AAA solar simulator,94023A-
U it is measured under the conditions of).
The compound structure that embodiment is related to is as follows:
The structure of embodiment 7-12 (respectively device PeSC 1-6) and the film thickness thickness of each layer are as follows:
PeSC 1:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-21(150nm)/MoO3(10nm)/Ag
(100nm)
PeSC 2:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-9(150nm)/MoO3(10nm)/Ag
(100nm)
PeSC 3:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-5(150nm)/MoO3(10nm)/Ag
(100nm)
PeSC 4:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-17(150nm)/MoO3(10nm)/Ag
(100nm)
PeSC 5:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-2(150nm)/MoO3(10nm)/Ag
(100nm)
PeSC 6:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/1-3(150nm)/MoO3(10nm)/Ag
(100nm)
Comparative example
The preparation method of comparative example 1 is identical as embodiment, is only to change hole mobile material, the device junction of comparative example 1
Structure is as follows:
PeSC 7:
FTO(150nm)/TiO2(100nm)/CH3NH3PbI3(250nm)/spiro-OMeTAD(150nm)/MoO3
(10nm)/Ag(100nm)
The performance data of device is as shown in table 1:
Table 1: device performance data
As seen from the above table, using the device of the compounds of this invention compared to the commercial materials spiro- generallyd use in the industry
OMeTAD hole mobile material can obtain comparable device efficiency, and the efficiency of some of devices has been even more than 20%.From
From the point of view of the synthesis purification step of material, the synthesis step and purification step relative ease of the compounds of this invention.
In conclusion the present invention is with indoles, simultaneously [3,2,1-jk] carbazole is core, by modifying all kinds of donor residues on it
Group is adjusted, and can get more matched energy level, higher hole mobility and higher thermal stability, thus energy with higher
Measure transfer efficiency.Its hole mobility is up to 6.5 × 10-4cm2V-1S-1, can be used as hole mobile material and apply in solar-electricity
It in the device of pond, can effectively inhibit the consume of energy, improve energy conversion efficiency, the device lifetime, electricity of solar cell device
The performances such as current density, fill factor and cut-in voltage.Have compared with commercialized spirofluorene derivative material spiro-OMeTAD
The energy conversion efficiency to compare favourably, wherein being no lack of the device efficiency more than spiro-OMeTAD.Also, with spiro-OMeTAD phase
Than due to greatly reducing production cost with relatively simple synthesis purification step, to reduce perovskite solar-electricity
The cost in pond.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of indoles simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that for the chemical combination indicated comprising following general formula (1)
Object:
Wherein, simultaneously simultaneously [3,2,1-jk] carbazole parent nucleus connects 3 R bases to the indoles in [3,2,1-jk] carbazole derivates to the indoles
Group, any one of aryl/heteroaromatic rings that the R group in each site is 6~30 independently selected from annular atom number；
In aryl/heteroaromatic rings that the annular atom number is 6~30, the hydrogen-based connecting with carbon atoms on a benzene ring is one or more
R1Group replaces；The R in each site1Group independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted carbon atom number be 1~
40 straight chained alkyl/alkoxy/thioalkyl groups, alternatively, branch or ring that substituted or unsubstituted carbon atom number is 3~40
Any one of alkyl/alkoxy/thioalkyl groups of shape.
2. indoles as described in claim 1 simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that be in the annular atom number
In 6~30 heteroaromatic rings, the hetero atom in each site is independently selected from any one of N, O or S.
3. indoles as claimed in claim 1 or 2 simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that the R in each site
Group is independently selected from any one of following general formula Ar-1 to Ar-11:
Wherein, the R in each site1Group is 1~40 independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted carbon atom number
Straight chained alkyl/alkoxy/thioalkyl groups, alternatively, substituted or unsubstituted carbon atom number be 3~40 branch or ring-type
Any one of alkyl/alkoxy/thioalkyl groups.
4. indoles as claimed in claim 1 or 2 simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that the R group is selected from
By the R1The substituted or unsubstituted pyridyl group of group, acridinyl, 9,9- dimethyl -10- phenyl-acridan base, pheno
Oxazines base, -10 hydrogen of 10- phenyl-phenoxazine base, phenothiazinyl, -10 hydrogen of 10- phenyl-phenothiazinyl, hexichol amido, triphenylamine
Base, dibenzofuran group, dibenzothiophene, dibenzothiophenes sulfuryl, diphenyl triazine radical, meta-terphenyl base, diphenyl are phonetic
Any in piperidinyl, two phenenyl phosphinyl, dimethylaminoborane base, tri-phenyl-silane base, triphenyl methane base, xenyl or naphthalene
Kind, the R in each site1The straight chained alkyl that group independently is hydrogen or carbon atom number is 1~4.
5. indoles as claimed in claim 4 simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that the R base in each site
Group is independently selected from by the R1The substituted or unsubstituted phenoxazine base of group, phenothiazinyl, hexichol amido, triphenylamine base, 9,
Any one of 9- dimethyl -10- phenyl -9,10- acridan base, -10 hydrogen of 10- phenyl-phenothiazinyl, the R in each site1Base
The straight chained alkyl that group independently is hydrogen or carbon atom number is 1~4.
6. indoles as described in claim 1 simultaneously [3,2,1-jk] carbazole derivates, which is characterized in that the compound be selected from
Any one of lower general formula 1-1 to 1-33:
7. the preparation method of indoles according to any one of claim 1 to 6 simultaneously [3,2,1-jk] carbazole derivates, special
Sign is, comprising the following steps:
By the indoles of 2,5 and 11 position functionals, simultaneously [3,2,1-jk] carbazole is carried out described in metal catalyzed coupling reaction introducing three
R group.
8. simultaneously [3,2,1-jk] carbazole derivates are being used to prepare electronics to indoles according to any one of claim 1 to 6
Application in device, which is characterized in that the electronic device is selected from organic electroluminescence device, organic field effect tube or calcium
Titanium ore solar battery.
9. a kind of electronic device, which is characterized in that have such as indoles described in any one of claims 1 to 6 simultaneously [3,2,1-
Jk] carbazole derivates.
10. electronic device as claimed in claim 9, which is characterized in that the electronic device is perovskite solar battery device
Part, the perovskite solar cell device include electron transfer layer, perovskite active layer and hole transmission layer, the perovskite
There are the indoles simultaneously [3,2,1-jk] carbazole derivates in solar cell device.
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| CN111004243A (en) * | 2019-12-02 | 2020-04-14 | 武汉华星光电半导体显示技术有限公司 | Indolo [3,2,1-jk ] carbazole derivative, organic electroluminescent device, and display panel |
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| CN114685533A (en) * | 2020-12-29 | 2022-07-01 | 维思普新材料（苏州）有限公司 | Indole [3,2,1-kl ] phenothiazine 5, 5-dioxide derivative and application thereof and electronic device |
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Application publication date: 20190920 |