CN109970768B - Based on carbazole eleven-membered condensed ring planar nucleus D (A-Ar)2Organic photoelectric compound, preparation method and application - Google Patents

Based on carbazole eleven-membered condensed ring planar nucleus D (A-Ar)2Organic photoelectric compound, preparation method and application Download PDF

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CN109970768B
CN109970768B CN201910284775.9A CN201910284775A CN109970768B CN 109970768 B CN109970768 B CN 109970768B CN 201910284775 A CN201910284775 A CN 201910284775A CN 109970768 B CN109970768 B CN 109970768B
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刘煜
高辉山
刘座吉
朱卫国
杨振
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Abstract

The invention relates to a D (A-Ar) based on carbazole eleven-element condensed ring planar nucleus2An organic photoelectric compound and a preparation method and application thereof. The ternary carbazole central ring unit is coupled with thiophene and benzothiophene derivatives through ring closing reaction and coupling reaction to obtain derivatives of the carbazole-containing eleven-element condensed ring conjugated planar structure aromatic compound and D (A-Ar) containing carbazole multi-condensed ring central nucleus2The linear organic micromolecule photovoltaic material. Derivatives of such eleven-membered large fused ring conjugated planar structure compounds and corresponding D (A-Ar)2The linear organic micromolecule photovoltaic material has high thermal stability and high hole mobility. Through the development and application of the material, high-efficiency organic solar cells, organic electroluminescent diodes, organic field effect transistors and organic near infrared photoelectric detector materials are obtained.

Description

Based on carbazole eleven-membered condensed ring planar nucleus D (A-Ar)2Organic photoelectric compound, preparation method and application
Technical Field
The invention relates in particular to a molecular backbone donor core comprising a carbazole eleven-membered fused ring planar core D (A-Ar)2The linear micromolecule material can be applied to the technical field of organic photoelectricity.
Background
Organic solar cells have become a hotspot in research in the photovoltaic field due to the advantages of low price, light weight, large-area preparation and the like.
As the organic micromolecule donor material in the photosensitive active layer for absorbing sunlight and converting the sunlight into electric energy, the organic micromolecule donor material has the outstanding advantages of simple purification, monodispersity, definite structure, easy modification, good batch reproducibility and the like, and has a wide market application prospect. Therefore, organic solar cells have attracted increasing attention.
At present, based on the scientific problems of narrow absorption spectrum, low carrier mobility, low efficiency, poor stability and the like of organic micromolecule solar cell materials, novel high-performance micromolecule donor materials need to be developed.
Disclosure of Invention
The invention aims to provide a carbazole-based undecene condensed ring planar core D (A-Ar)2The organic photoelectric compound derivative is obtained through ring closing and coupling reaction. Provides a carbazole-based eleven-membered fused ring conjugated planar nucleus with better coplanarity, wide ultraviolet absorption and high mobility and D (A-Ar)2A derivative structure small molecular material and application thereof in an organic photoelectric device. The micromolecule material has the characteristics of definite molecular structure, easiness in modification, good batch repeatability, good molecular planarity, wider ultraviolet absorption, higher mobility and the like, can improve the charge collection capacity, short-circuit current and filling factor of an organic battery device, and has important potential in the aspect of improving the energy conversion efficiency of the battery device.
The invention relates to a carbazole-based eleven-membered condensed ring conjugated planar nucleus and a D (A-Ar) thereof2The derivative is mainly characterized in that: based on carbazole eleven-element condensed ring conjugate plane center as donor core (D), conjugated structure with electron-withdrawing property is A unit and terminal condensed ring aromatic hydrocarbon unit Ar, D (A-Ar) is constructed through even chain reaction2Linear organic small molecule derivative donor material.
The technical scheme of the invention is as follows:
carbazole-containing eleven-membered condensed ring conjugated plane donor nucleus and D (A-Ar) thereof2Linear small molecules of the type having the following structure:
Figure GDA0002694488270000021
wherein R is independently selected from C16～C20A branched alkyl group;
d is a conjugated plane central core based on the carbazole eleven-membered fused ring, and X is an S, O or Se atom;
wherein A is a conjugated unit with electron-withdrawing property, and the conjugated unit A is thiophene pyrrolo-pyrrole-dione, thiazole pyrrolo-pyrrole-dione, phenyl pyrrolo-pyrrole-dione, pyridine pyrrolo-pyrrole-dione, isoindigo, pyridine isoindigo, thiophene isoindigo, bithiophene [3,4-b ] pyrrole-dione, perylene imide, naphthalimide, thieno [4,5-b ] pyridone, difluo-thieno [4,5-b ] pyridone, monofluorobenzothiadiazole, difluobenzothiadiazole, monochlorobenzothiadiazole, dichlorinated benzothiadiazole, alkoxybenzothiadiazole, pyridothiadiazole, monofluorobenzselenadiazole, dichlorinated benzoselenadiazole, alkoxybenzoselenadiazole, pyridoselenadiazole, thieno [3,4-b ] benzo-3-fluoro-thienyl ester, thiophene [3,4-b ] selenadiazole ester, thiophene [4,5-b ] selenadiazole, and the like, Thiophene [3,4-b ] and-3-chloro-thiophene ester, thiophene [3,4-b ] and-3-fluoro-thiophene ketone, thiophene [3,4-b ] and-3-chloro-thiophene ketone, benzodithiadiazole, benzene [2,3-c ] pyrrole dione, thiophene [2,3-c ] pyrrole dione, benzodithiophene dione, difluoride benzotriazole, dichlorine benzotriazole, one of fluorinated, chlorinated and alkoxylated quinoxaline or one of derivatives thereof;
further, the a-conjugated unit has one of the following structures:
Figure GDA0002694488270000031
further, the conjugated acceptor unit A may be modified with an alkyl chain, R1Independently selected from C6～C12Straight or branched chain alkyl.
Wherein Ar is a hydrogen atom, a fluorine atom or a functionalized terminal conjugated donor unit. The conjugated unit of Ar is dialkyl thiophene, 4-fluoro-2-alkyl thiophene, 3, 4-difluoro-2-alkyl thiophene, 2-alkyl mercapto-thiophene, 2-alkyl thiazole, 2-alkyl mercapto thiazole, 4-chloro-2-alkyl thiophene, 2-alkyl stannophene, 2-alkyl mercapto selenophene, 2-alkyl selenazole, 2-alkyl mercapto selenazole, 4-fluorobenzene, 2, 4-difluorobenzene, 4-alkyl benzene, 4-alkoxy benzene, benzo [ b ] thiophene, benzo [ b ] furan, benzo [ b ] selenazole, benzo [ b ] tellurium oxazole, alkyl thieno [3,2-b ] thiophene, alkyl mercapto thieno [3,2-b ] thiophene, 2-or 3-9-alkyl carbazole, 2-or 3-9, 9-dialkylfluorene, triarylamine, 2-naphthalene, 2-anthracene, 2-phenanthrene or 2-pyrene;
go toStep one, Ar is a functionalized terminal conjugated donor unit, Ar can be modified by an alkyl chain, R1Independently selected from C6～C12A linear or branched alkyl group having one of the following structures:
Figure GDA0002694488270000041
further, D is a carbazole-based undecene-membered fused ring conjugated planar central core donor unit having one of the following structures:
Figure GDA0002694488270000042
d (A-Ar) based on carbazole eleven-element condensed ring plane central nucleus2The organic photoelectric compound is used as an active layer material and applied to an organic photovoltaic device.
Compared with the prior art, the invention has the following advantages:
1) the invention synthesizes D (A-Ar) based on carbazole eleven-element condensed ring conjugate plane central nucleus2The conjugated micromolecule has the characteristics of definite structure, definite molecular weight, high batch repeatability and the like, can be dissolved by using solvents such as chloroform, tetrahydrofuran, chlorobenzene, o-dichlorobenzene and the like, can be processed as an active layer soluble solution, and has great advantages in the aspect of large-area production of future organic photovoltaic devices.
2) The invention synthesizes D (A-Ar) based on carbazole eleven-element condensed ring conjugate plane central nucleus2The conjugated micromolecules have excellent plane performance, good charge extraction performance, wider ultraviolet absorption and good molar absorption coefficient, and can improve the filling factor, short-circuit current and energy conversion efficiency of a battery device.
3) The invention synthesizes D (A-Ar) based on carbazole eleven-element condensed ring conjugate plane central nucleus2The conjugated micromolecules have certain advantages in the aspects of manufacturing thick-film interface materials and devices, and have great potential in large-area production of organic solar cells in the future.
4)The materials of the invention are described in classical D (A-Ar)2On the basis of the structure, by introducing a polycyclic aromatic hydrocarbon D unit with a carbazole planar structure with hole transport performance, the molecular construction of an organic photovoltaic donor material with narrow band gap, wide spectral band response and high mobility and the application of the organic photovoltaic donor material in a solvent processing type bulk heterojunction organic solar cell are realized. Such D (A-Ar)nThe molecular structure of the type structure material may be any of the following molecules.
Figure GDA0002694488270000051
Formula ITBTDBC (DPP)2
Figure GDA0002694488270000052
Formula IITBTDBC (DPP-Cz)2
Figure GDA0002694488270000061
Formula IIITBTDBC (DPP-Th)2
Figure GDA0002694488270000062
Formula IVTBTDBC (DPP-ST)2
D (A-Ar) based on the dodecameric fused-ring conjugated planar central nucleus of carbazole2The linear organic small molecule photovoltaic material comprises any of the following derivatives:
d- (A-Ar) taking carbazole eleven-membered fused ring conjugated plane central core as donor unit (D), pyrrolopyrroledione derivative as electron-withdrawing group (A) and terminal (Ar) as H atom2Linear micromolecular photovoltaic material TBTDBC (DPP)2。
Taking a carbazole eleven-membered fused ring conjugated plane central core as a donor unit (D), a pyrrolopyrroledione derivative as an electron withdrawing group (A), and an end (Ar) asD- (A-Ar) of 3-position-9-octylcarbazole2Type linear small molecule photovoltaic material TBTDBC (DPP-Cz)2。
D- (A-Ar) taking carbazole eleven-membered fused ring conjugated plane central core as donor unit (D), pyrrolopyrroledione derivative as electron-withdrawing group (A) and 5-octylthiophene as terminal (Ar)2Type linear small molecule photovoltaic material TBTDBC (DPP-Th)2。
D- (A-Ar) taking carbazole eleven-membered fused ring conjugated plane central core as donor unit (D), pyrrolopyrroledione derivative as electron-withdrawing group (A) and 5-octylmercapto thiophene as terminal (Ar)2Linear micromolecule photovoltaic material TBTDBC (DPP-ST)2。
In order to obtain the material, the preparation scheme of the material is as follows:
the D (A-Ar)2The synthesis of a planar central core (D) of the molecular photovoltaic material, namely TBTDBC (mainly comprises the following three steps):
1) firstly, dissolving alkylated 2, 7-dibromo-3, 6-diiodo-carbazole in toluene, adding 2.0 mol of 2-trimethylstannylbenzene [ b ] thiophene with equivalent weight and 1-5% of tetrakis (triphenylphosphine) palladium into an inert gas environment, heating, refluxing, reacting overnight, extracting after the reaction is finished, drying, and purifying by column chromatography to obtain an intermediate 3, 6-bis (benzothiophen-2-yl) -2, 7-dibromo-9- (2-octyldodecyl) -9-carbazole.
2) And secondly, dissolving the intermediate 3, 6-bis (benzothiophen-2-yl) -2, 7-dibromo-9- (2-octyldodecyl) -9-carbazole in toluene, adding 2-3 molar equivalents of 2-trimethyltin thiophene and 1-5% of tetrakis (triphenylphosphine) palladium, and carrying out heating reflux reaction for 2-10 hours. After the reaction is finished, the intermediate product 3, 6-bis (benzothiophen-2-yl) -9- (2-octyldodecyl) -2, 7-bis (thiophene-2-yl) -9-carbazole is obtained by concentration, extraction, drying and column chromatography purification.
3) And thirdly, adding the intermediate product 3, 6-bis (benzothiophen-2-yl) -9- (2-octyldodecyl) -2, 7-bis (thiophene-2-yl) -9-carbazole into dichloromethane for dissolving, simultaneously adding 1-2 mL of nitromethane, reacting at room temperature for 5-8 hours under the protection of inert gas and under the closed condition and the irradiation of ultraviolet light of 275nm, adding a saturated ammonium chloride solution after the reaction is finished, extracting, drying, purifying by column chromatography, and recrystallizing to obtain the central donor core TBTDBC.
Preparing TBTDBC- [ Sn (CH) by stannization of material central core TBTDBC3)3]2：
Adding the obtained central donor nucleus TBTDBC into an anhydrous tetrahydrofuran solution for dissolving, cooling to-78 ℃ under the protection of inert gas, slowly dripping n-butyllithium (0.97mL, 1.55mmol and 1.6M) solution into the anhydrous tetrahydrofuran solution for reaction for 3h, and adding SnBu3Cl was added rapidly and after 1 hour of further reaction, the reaction was transferred to room temperature and allowed to react for 16 hours. After quenching with water, extraction was carried out. The solvent is removed by rotary decompression to obtain a yellow viscous crude product. Separating the crude product by neutral alumina column chromatography, drying with anhydrous magnesium sulfate, filtering, removing solvent by rotary evaporation under reduced pressure, and eluting with dichloromethane and petroleum ether to obtain stannic yellow viscous solid TBTDBC- [ Sn (CH)3)3]2。
The D (A-Ar)2Synthesizing a side chain receptor A of the linear molecular photovoltaic material:
D(A-Ar)2the side chain Br-DPP synthesis of linear micromolecule photovoltaic material is directly purchased from Shanghai' an Ji-resistant chemical company Limited.
D(A-Ar)2Synthesizing a side chain Br-DPP-Cz of the linear micromolecule photovoltaic material, namely sequentially adding Br-DPP, 2M potassium carbonate aqueous solution and 9-octyl-3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -carbazole into a toluene solvent, carrying out suzuki coupling reaction under the protection of nitrogen, and carrying out column chromatography separation to obtain a DPP-Cz purple solid; under the dark environment condition and ice bath, the DPP-Cz purple solid and a corresponding amount of NBS are sequentially added, reaction is carried out for 6 hours, and the purple solid Br-DPP-Cz is obtained through column chromatography separation.
D(A-Ar)2The preparation method of the side chain Br-DPP-Th of the linear small-molecule photovoltaic material comprises the steps of sequentially adding Br-DPP, 2M potassium carbonate aqueous solution and 5-octyl-2-tributylstannyl thiophene into a toluene solvent, carrying out stille coupling reaction under the protection of nitrogen, and carrying out column chromatography separation to obtain the side chain DPP-Th purple of a target moleculeA solid; under the dark environment condition and ice bath, sequentially adding DPP-Th purple solid and a corresponding amount of NBS, reacting for 6 hours, and separating by column chromatography to obtain the purple black solid Br-DPP-Th.
D(A-Ar)2Synthesizing a side chain Br-DPP-ST of the linear micromolecule photovoltaic material, namely adding Br-DPP, 2M potassium carbonate aqueous solution and 5-octylmercapto-2-tributylstannyl thiophene into a toluene solvent in sequence, performing stille coupling reaction under the protection of nitrogen, and performing column chromatography separation to obtain a side chain DPP-ST purple solid of a target molecule; under the dark environment condition and ice bath, adding DPP-ST purple solid and NBS with corresponding amount in sequence, reacting for 6 hours, and separating by column chromatography to obtain the purple black solid Br-DPP-ST.
D(A-Ar)2Small molecule photovoltaic material target molecule TBTDBC (DPP)2The synthesis of (2): in a toluene solvent, a side chain Br-DPP and a central nuclear tin reagent TBTDBC- [ Sn (CH) are added in sequence3)3]2Under the protection of nitrogen, and under the catalysis of palladium tetratriphenylphosphine, stille coupling reaction is carried out to synthesize D (A-Ar)2Linear micromolecule photovoltaic material target compound TBTDBC (DPP)2And the crude product is separated by column chromatography to obtain a pure product.
D(A-Ar)2Small molecule photovoltaic material target molecule TBTDBC (DPP-Cz)2The synthesis of (2): adding side chain Br-DPP-Cz and central core tin reagent TBTDBC- [ Sn (CH) in toluene solvent3)3]2Under the protection of nitrogen, and under the catalysis of palladium tetratriphenylphosphine, stille coupling reaction is carried out to synthesize D (A-Ar)2Linear micromolecule photovoltaic material target compound TBTDBC (DPP-Cz)2And the crude product is separated by column chromatography to obtain a pure product.
D(A-Ar)2Type small molecule photovoltaic material target molecule TBTDBC (DPP-Th)2The synthesis of (2): in a toluene solvent, a side chain Br-DPP-Th and a central core tin reagent TBTDBC- [ Sn (CH) are added in sequence3)3]2Under the protection of nitrogen, and under the catalysis of palladium tetratriphenylphosphine, stille coupling reaction is carried out to synthesize D (A-Ar)2Linear micromolecule photovoltaic material target compound TBTDBC (DPP-Th)2The crude product is separated by column chromatography to obtainAnd (5) purifying.
D(A-Ar)2Small molecule photovoltaic material target molecule TBTDBC (DPP-Cz)2The synthesis of (2): adding side chain Br-DPP-ST and central core tin reagent TBTDBC- [ Sn (CH) in toluene solvent3)3]2Under the protection of nitrogen, and under the catalysis of palladium tetratriphenylphosphine, stille coupling reaction is carried out to synthesize D (A-Ar)2Linear micromolecule photovoltaic material target compound TBTDBC (DPP-ST)2And the crude product is separated by column chromatography to obtain a pure product.
D (A-Ar) of the present invention2Compared with most of the disclosed small molecule photovoltaic materials, the small molecule photovoltaic material is characterized in that: (1) design D (A-Ar) due to planar molecular StructurenThe small molecular material has better film-forming property; (2) due to the introduction of the large plane unit TBTDBC at the conjugated center, the small molecular material has narrower band gap and wider spectral band response; (3) the target small molecule has stronger intermolecular pi-pi accumulation effect; and (4) due to the existence of a push-pull structure in the molecule, the delocalization degree of the target small molecule is high, the intermolecular acting force and the charge transmission capability of the molecule can be enhanced, and the transmission of device electrons is facilitated. Therefore, the material is an organic small molecule photovoltaic material with great development prospect.
The application of the invention is that: the photovoltaic material designed and synthesized is used as a donor to react with PC71BM are mixed under different ratios to manufacture a photovoltaic device, so that solar energy is well converted into electric energy.
The organic micromolecular photovoltaic material is used for manufacturing a bulk heterojunction organic solar cell device, and the device structure is Glass/ITO/ZnO (30nm)/Compounds: PC71BM(20nm)/MoO3(10nm)/Ag (100 nm). Comprises an indium tin oxide conductive glass substrate layer (ITO) and a ZnO anode layer. Wherein the anode modification layer is a poly ethylenedioxythiophene (PEDOT, 30nm) coating; cathode is MoO3(10nm)/Ag (100nm) deposition layer; the material of the active layer is D (A-Ar)nMolecule and PC71BM in a blending weight ratio of 1:1.5(w/w,20 mg/mL).
The hole mobility of the device is Glass/ITO/PEDOT: PSS (10 n)m)/active layer(20 nm)/MoO3(10nm)/Au (100 nm).
Drawings
FIG. 1 shows TBTDBC (DPP) of the present invention2Graph of thermal weight loss
FIG. 2 shows TBTDBC (DPP)2UV-VISIBLE ABSORPTION SPECTRUM IN DICHLOROETHANE SOLUTION
FIG. 3 shows TBTDBC (DPP)2UV-VIS absorption spectrum in solid film
FIG. 4 shows TBTDBC (DPP)2Cyclic voltammogram on solid films
FIG. 5 shows TBTDBC (DPP)2And PC71J-V plot at 1:1.5(w/w,20mg/mL) BM mix ratio
FIG. 6 shows TBTDBC (DPP)2And PC71EQE curve chart under the condition that the mixing ratio of BM is 1:1.5(w/w,20mg/mL)
FIG. 7 shows TBTDBC (DPP)2And PC71J-V characteristic curve diagram of blend film single-hole device of BM
FIG. 8 shows TBTDBC (DPP-Cz) of the present invention2Graph of thermal weight loss
FIG. 9 shows TBTDBC (DPP-Cz) of the present invention2UV-VISIBLE ABSORPTION SPECTRUM IN DICHLOROETHANE SOLUTION
FIG. 10 shows TBTDBC (DPP-Cz) of the present invention2UV-VIS absorption spectrum in solid film
FIG. 11 shows TBTDBC (DPP-Cz) of the present invention2Cyclic voltammogram on solid films
FIG. 12 shows TBTDBC (DPP-Cz) of the present invention2And PC71J-V plot at 1:1.5(w/w,20mg/mL) BM mix ratio
FIG. 13 shows TBTDBC (DPP-Cz) of the present invention2And PC71EQE curve chart under the condition that the mixing ratio of BM is 1:1.5(w/w,20mg/mL)
FIG. 14 shows TBTDBC (DPP-Cz) of the present invention2And PC71J-V characteristic curve diagram of blend film single-hole device of BM
FIG. 15 shows TBTDBC (DPP-Th) according to the present invention2Graph of thermal weight loss
FIG. 16 shows TBTDBC (DPP-Th) according to the present invention2UV-VISIBLE ABSORPTION SPECTRUM IN DICHLOROETHANE SOLUTION
FIG. 17 shows TBTDBC (DPP-Th) according to the present invention2UV-VIS absorption spectrum in solid film
FIG. 18 shows TBTDBC (DPP-Th) according to the present invention2Cyclic voltammogram on solid films
FIG. 19 shows TBTDBC (DPP-Th) according to the present invention2And PC71J-V plot at 1:1.5(w/w,20mg/mL) BM mix ratio
FIG. 20 shows TBTDBC (DPP-Th) according to the present invention2And PC71EQE curve chart under the condition that the mixing ratio of BM is 1:1.5(w/w,20mg/mL)
FIG. 21 shows TBTDBC (DPP-Th) according to the present invention2And PC71J-V characteristic curve diagram of blend film single-hole device of BM
FIG. 22 shows TBTDBC (DPP-ST) according to the present invention2Graph of thermal weight loss
FIG. 23 shows TBTDBC (DPP-ST) according to the present invention2UV-VISIBLE ABSORPTION SPECTRUM IN DICHLOROETHANE SOLUTION
FIG. 24 shows TBTDBC (DPP-ST) according to the present invention2UV-VIS absorption spectrum in solid film
FIG. 25 shows TBTDBC (DPP-ST) according to the present invention2Cyclic voltammogram on solid films
FIG. 26 shows TBTDBC (DPP-ST) according to the present invention2And PC71J-V plot at 1:1.5(w/w,20mg/mL) BM mix ratio
FIG. 27 shows TBTDBC (DPP-ST) according to the present invention2And PC71EQE curve chart under the condition that the mixing ratio of BM is 1:1.5(w/w,20mg/mL)
FIG. 28 shows TBTDBC (DPP-ST) according to the present invention2And PC71J-V characteristic curve diagram of blend film single-hole device of BM
FIG. 29 shows TBTDBC (DPP)2Mass spectrum of
FIG. 30 shows TBTDBC (DPP-Cz) of the present invention2Mass spectrum of
FIG. 31 shows TBTDBC (DPP-Th) according to the present invention2Mass spectrum of
FIG. 32 shows TBTDBC (DPP-ST) according to the present invention2Mass spectrum of
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention in any way.
Example 1
D (A-Ar) based on carbazole eleven-membered condensed ring central nucleus2The synthetic route of the intermediate (DPP-Cz, Br-DPP-Cz, DPP-Th, Br-DPP-Th, DPP-ST and Br-DPP-ST) of the linear small molecule of the organic photoelectric compound is shown as the following formula.
Figure GDA0002694488270000111
Synthesis of 1, 2, 5-bis- (2-hexyldecyl) -3- (5- (9-octylcarbazol-3-yl) thiophen-2-yl) -6- (thiophen-2-yl) pyrrolo [3,4-c ] pyrrole-1, 4-dione (DPP-Cz)
2, 5-bis (2-hexyldecyl) -3- (5-bromothien-2-yl) -6- (thien-2-yl) pyrrolo [3,4-c ] is added sequentially to a 100mL dry three-necked flask]Pyrrole-1, 4-dione (Br-DPP) (0.50g, 0.60mmol), tetrakis (triphenylphosphine) palladium (Pd (PP) in 30mL of toluene3)435mg, 0.03mmol), 9-octyl-3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -carbazole (267mg, 0.66mmol), potassium carbonate solution (2M, 3mL) and Aliquant 336(4 drops). Refluxing for 24h, cooling, extracting with 3 × 25mL of chloroform, combining organic phases, washing with 3 × 40mL of saturated saline solution, drying the organic phase with anhydrous magnesium sulfate, filtering, removing the solvent by spinning, performing column chromatography on the crude product by using silica gel as a stationary phase and dichloromethane and petroleum ether as eluents according to the volume ratio of 1: 4. A purple solid (334mg, yield 54%) was obtained.1H NMR (400MHz,CDCl3)(PPM):9.04(d,J＝4.1Hz,1H),8.85(d,J＝2.9Hz,1H),8.39(d, J＝1.5Hz,1H),8.16(d,J＝7.6Hz,1H),7.80(m,1H),7.60(d,J＝4.1Hz,1H), 7.54–7.47(m,2H),7.43(d,J＝8.7Hz,2H),7.29(d,J＝8.6Hz,2H),4.32(t,J＝7.1 Hz,2H),4.11(d,J＝7.6Hz,2H),4.05(d,J＝7.7Hz,2H),2.05(m,1H),1.99–1.82 (m,3H),1.46–1.30(m,16H),1.23(m,41H),0.84(m,16H).
Synthesis of 2,3- (5-bromothien-2-yl) -2, 5-bis- (2-hexyldecyl) -3-6- (5- (9-octyl-carbazol-3-yl) thien-2-yl) -pyrrolo [3,4-c ] pyrrole-1, 4-dione (Br-DPP-Cz)
The compound DPP-CZ (334mg, 0.33mmol) and 20mL of chloroform were added sequentially in a 100mL dry three-necked flask, and a chloroform solution containing NBS (59mg, 0.33mmol) dissolved therein was slowly added dropwise from a constant-pressure dropping funnel under magnetic stirring in an ice bath and in a dark environment. After the completion of the dropwise addition, the reaction was quenched with 20mL of water after 6 hours, and extracted with 3X 25mL of chloroform. Drying the organic phase by anhydrous magnesium sulfate, filtering, removing the solvent by rotation, taking silica gel as a stationary phase, and adding methane with the volume ratio of 1: 3: column chromatography using petroleum ether as eluent gave a purple solid (335mg, yield 93%).1H NMR(400 MHz,CDCl3)(PPM):9.06(d,J＝4.1Hz,1H),8.58(d,J＝4.1Hz,1H),8.38(d,J＝ 1.3Hz,1H),8.15(d,J＝7.6Hz,1H),7.79(d,J＝8.6,1H),7.51(m,2H),7.43(d,J＝ 8.4,2H),7.29(d,J＝7.8Hz,1H),7.21(d,J＝4.2Hz,1H),4.31(t,J＝7.1Hz,2H), 4.09(d,J＝7.6Hz,2H),3.96(d,J＝7.6Hz,2H),2.03(m,1H),1.96–1.82(m,3H), 1.45–1.03(m,53H),0.85(m,20H).
Synthesis of 3,2, 5-bis- (2-hexyldecyl) -3- [ 5-9-octyl- (2, 2-dithienyl) -5-yl ] -6 (thien-2-yl) pyrrolo [3,4-c ] pyrrole-1, 4-dione (DPP-Th)
2, 5-bis (2-hexyldecyl) -3- (5-bromothien-2-yl) -6- (thien-2-yl) pyrrolo [3,4-c ] is added sequentially to a 100mL dry three-necked flask]Pyrrole-1, 4-dione Br-DPP (0.50g, 0.60mmol), 30mL toluene, tetrakis (triphenylphosphine) palladium (Pd (PP)3)435mg, 0.03mmol) and 5-octyl-2-tributylstannyl thiophene (321mg, 0.66 mmol). Heating to 110 ℃ under the protection of nitrogen, refluxing for 24 hours, and cooling the reaction system to room temperature. After quenching the reaction system with 10mL of diluted hydrochloric acid, the reaction system was extracted three times (20mL of chloroform). Mixing organic phases, washing with 3 × 40mL saturated saline solution, drying the organic phase with anhydrous magnesium sulfate, filtering, removing the solvent by rotary evaporation under reduced pressure, separating the crude product by column chromatography with silica gel as stationary phase and dichloromethane and petroleum ether as eluent in a volume ratio of 1:4 to obtainTo a purple solid (420mg, yield 74%).1H NMR(400MHz,CDCl3)(ppm):8.93(d,J＝4.1Hz,1H),8.85(d,J ＝3.9,1H),7.60(d,J＝8.3,1H),7.31–7.20(m,2H),7.14(d,J＝3.6Hz,1H),6.74(d, J＝3.6Hz,1H),4.02(m,4H),2.82(t,J＝7.6Hz,2H),1.93(m,2H),1.70(m,2H), 1.26(m,58H),0.9–0.75(m,15H).
Synthesis of 4, 3- (5-bromothien-2-yl) -2, 5-bis- (2-hexyldecyl) -6- (5- (octyl) - [2, 2-dithienyl ] -5-yl) pyrrolo [3,4-c ] pyrrole-1, 4-dione (Br-DPP-Th)
A100 mL dry three-necked flask was charged with DPP-Th compound (420mg, 0.45mmol) and 20mL chloroform in this order, and then under magnetic stirring and ice-bath conditions, a chloroform solution containing NBS (80mg,0.45mmol) dissolved therein was slowly added dropwise in the dark. After the dropwise addition, the reaction system was quenched with 20mL of water after 6h, and the reaction system was extracted three times (20mL of chloroform). The combined organic phases were washed with 3X 40mL of saturated brine, the organic phases were dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure, and the crude product was separated by column chromatography using silica gel as the stationary phase and dichloromethane to petroleum ether as the eluent in a volume ratio of 1:3 to give a violet solid (432mg, yield 95%).1HNMR(400MHz,CDCl3)(ppm):8.95(d,J＝ 1.7Hz,1H),8.58(d,J＝4.1Hz,1H),7.22(d,4.1Hz,2H),7.15(d,J＝3.2Hz,1H), 6.74(s,1H),4.01(d,J＝7.3Hz,2H),3.94(d,J＝7.4Hz,2H),2.78(m,2H),1.92(m, 2H),1.8–1.63(m,2H),1.34–1.19(m,58H),0.89–0.82(m,15H).
Synthesis of 5, 2, 5-bis- (2-hexyldecaalkyl) -3- [5- (octylmercapto) - (2, 2-dithienyl) -5-yl ] -6 (thien-2-yl) pyrrolo [3,4-c ] pyrrole-1, 4-dione (DPP-ST)
The compound 2, 5-bis (2-hexyldecyl) -3- (5-bromothien-2-yl) -6- (thien-2-yl) pyrrolo [3,4-c ] was added sequentially to a 100mL dry three-necked flask]Pyrrole-1, 4-dione Br-DPP (0.50g, 0.60mmol), 30mL toluene, tetrakis (triphenylphosphine) palladium (Pd (PP)3)435mg, 0.03mmol) and 5-octylmercapto-2-tributylstannyl thiophene (342mg, 0.66 mmol). Heating to 110 ℃ under the protection of nitrogen, refluxing for 24 hours, and cooling the reaction system to room temperature. Quenching the reaction system by using 10mL of dilute hydrochloric acid, and extracting for three timesThe reaction system was taken (20mL of chloroform). The organic phases were combined, washed with 3X 40mL of saturated brine, dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and the crude product was separated by column chromatography using silica gel as the stationary phase and dichloromethane to petroleum ether as the eluent in a volume ratio of 1:4 to give 410mg of a purple solid, yield 70%).1H NMR(400MHz,CDCl3)(ppm):8.89(m,4.0Hz,2H), 7.62(d,J＝5.0Hz,1H),7.27(d,J＝6.7Hz,2H),7.17(d,J＝3.7Hz,1H),7.03(d,J ＝3.7Hz,1H),4.02(m,4H),2.91–2.81(m,2H),1.93(m,2H),1.68–1.62(m,2H), 1.37–1.17(m,58H),0.94–0.81(m,15H).
Synthesis of 3- (5-bromothien-2-yl) -2, 5-bis- (2-hexyldecyl) -6- (5- (octylmercapto) - [2, 2-dithienyl ] -5-yl) pyrrolo [3,4-c ] pyrrole-1, 4-dione (Br-DPP-ST)
A100 mL dry three-necked flask was charged with DPP-ST (410mg, 0.42mmol) compound and 20mL chloroform in this order, and under magnetic stirring and ice-bath conditions, a chloroform solution containing NBS (75mg, 0.42mmol) dissolved therein was slowly added dropwise in the dark. After the dropwise addition, the reaction system was quenched with 20mL of water after 6h of reaction, and the reaction system was extracted three times (20mL of chloroform). The combined organic phases were washed with 3X 40mL of saturated brine, the organic phases were dried over anhydrous magnesium sulfate, filtered and the solvent was removed under reduced pressure, and the crude product was separated by column chromatography using silica gel as the stationary phase and dichloromethane to petroleum ether as the eluent in a volume ratio of 1:3 to give a purple solid (426mg, yield 96%).1H NMR(400MHz,CDCl3)(ppm): 8.92(d,J＝4.2Hz,1H),8.62(d,J＝4.2Hz,1H),7.26(d,J＝4.4Hz,1H),7.22(d,J ＝4.2Hz,1H),7.17(d,J＝3.7Hz,1H),7.03(d,J＝3.8Hz,1H),4.01(d,J＝7.6Hz, 2H),3.94(d,J＝7.6Hz,2H),2.86(m,2H),1.89(s,2H),1.65(m,2H),1.26(m,58H), 0.93–0.80(m,15H).
Example 2
Based on D (A-Ar)2Carbazole deca-unary condensed ring central nuclear tin reagent TBTDBC- [ Sn (CH) of organic photoelectric compound3)3]2The synthetic route of (A) is shown in the following formula.
Figure GDA0002694488270000151
Synthesis of 1, 2, 7-dibromo-3, 6-diiodo-9- (2-octyldodecyl) carbazole (M1)
2, 7-dibromo-carbazole (3g,4.97mmol) and 50mL of acetic acid are sequentially added into a 100mL three-necked flask, nitrogen is introduced for deoxidation and replacement for three times, the reactants are dissolved under magnetic stirring at 80 ℃, potassium iodide (2.22 g,13.41mmol) and potassium periodate (1.43g,6.71mmol) are rapidly weighed and are sequentially added into a reaction system, and reflux reaction is carried out for 12 hours. After completion of the reaction, it was cooled to room temperature, and the mixture was quenched by pouring into 100mL of water and washed with chloroform (100 mL. times.3) and saturated sodium sulfite solution (100 mL. times.3). The organic phases were combined and over anhydrous MgSO4Drying overnight, filtering, and removing the solvent under reduced pressure to obtain a grey crude product. The concentrated crude product was subjected to silica gel column chromatography using Petroleum Ether (PE) as an eluent to give a white solid (3.5g, yield 83%).1H NMR(CDCl3,400MHz),(ppm):8.46(s,1H),7.65(s,1H),4.00(d, J＝4.0Hz,2H),2.02(s,1H),0.86-1.21(m,23H).MALDI-MS(m/z):854.951for [M+].
2.2 Synthesis of 2,3, 6-bis (benzothien-2-yl) -2, 7-dibromo-9- (2-octyldodecyl) -9-carbazole (M2) Compound M1(3g,3.5mmol) was dissolved in 60mL of toluene, and tetrakis (triphenylphosphine) palladium (Pd (PP)3)4202mg, 0.18 mmol). Under the protection of nitrogen, the mixture was magnetically stirred, and 2-tributylmethyltin benzothiophene (3.0g, 7.0mmol) was slowly added dropwise at 80 ℃. After the dropwise addition, the temperature is raised to 110 ℃, reflux reaction is carried out for 24 hours, and the reaction liquid is cooled. After quenching with 100mL of dilute hydrochloric acid, the reaction was extracted three times (30mL of dichloromethane). Drying with anhydrous magnesium sulfate, filtering, and removing the solvent by rotary removal under reduced pressure to obtain a light yellow crude product. And (3) carrying out column chromatography separation on the crude product, and using dichloromethane to petroleum ether with the volume ratio of 1:20 as an eluent. Finally, a pale yellow, viscous solid was obtained (1.28g, yield 42%).1H NMR(400MHz,CDCl3)(ppm):8.23 (s,2H),7.90(d,J＝7.6Hz,2H),7.86(d,J＝7.3Hz,2H),7.74(s,2H),7.51(s,2H), 7.40(m,4H),4.16(d,J＝7.5Hz,2H),2.17(m,1H),1.49–1.37(m,7H),1.35–1.23 (m,25H),0.90(m,6H).
2.3 Synthesis of 9- (2-octyldodecyl) -2, 7-bis (thien-2-yl) -3, 6-bis (benzothien-2-yl) carbazole (M3)
Compound M2(1g, 1.2mmol) was dissolved in 40mL of toluene, followed by the addition of tetrakis (triphenylphosphine) palladium (Pd (PP)3)467mg, 0.06mmol) and 2-tributylstannyl thiophene (0.99g, 2.64 mmol). Heating to 110 ℃ under the protection of nitrogen, refluxing for 36 hours, and then slowly cooling the reaction system. After quenching with 40mL of dilute hydrochloric acid, the reaction was extracted three times (30mL of dichloromethane). Drying with anhydrous magnesium sulfate, filtering, and removing the solvent by rotary removal under reduced pressure to obtain a light yellow crude product. The crude product was subjected to column chromatography with dichloromethane: the petroleum ether volume ratio of 1:6 is used as eluent. Yellow viscous solid (0.72g, yield 72%) was obtained.1H NMR(400 MHz,CDCl3)(ppm):8.31(s,2H),7.80(d,J＝7.8Hz,2H),7.74(d,J＝7.9Hz,2H), 7.57(s,2H),7.40–7.30(m,6H),7.22(s,2H),7.02(m,4H),4.25(d,J＝6.9Hz,2H), 2.23(m,1H),1.43–1.38(m,6H),1.25(m,26H),0.90(m,6H).
2.4 Synthesis of planar Central core TBTDBC
Compound M3(0.70g, 0.80mmol) was dissolved in 60mL of dry dichloromethane, and the reaction was placed in an ice bath under nitrogen and magnetically stirred for 10 min. Anhydrous ferric chloride (0.90g, 5.6mmol) dissolved in 1.0mL of dry nitromethane is slowly dripped into a reaction system, the reaction system reacts for 5-8 hours at room temperature under the irradiation of 375 nm ultraviolet light, then 40mL of anhydrous methanol is added into the reaction system, and the reaction is carried out for 30 min. The reaction mixture was washed with saturated ammonium chloride solution (30mL) and extracted three times with dichloromethane (30 mL). The crude product was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. And (3) carrying out column chromatography separation on the crude product, wherein the used eluent is dichloromethane: the petroleum ether is 1: 4. This finally gave a yellow solid (0.56g, yield 80%).1H NMR(400MHz,CDCl3)(ppm):8.42(s,2H),8.20(s,2H), 8.02(s,2H),7.91(s,2H),7.59(s,2H),7.46(s,4H),7.35(s,2H),3.81(s,2H),2.07(s, 1H),1.31(m,10H),1.18(m,22H),0.84(m,6H).
2.5 tin-based Compound of the central nucleus TBTDBC- [ Sn (CH)3)3]2Synthesis of (2)
Compound TBTDBC (0.32g, 0.37mmol) was dissolved in 50mL of dry tetrahydrofuran, and a solution of n-butyllithium (0.97mL, 1.55mmol, 1.6M) was slowly added dropwise thereto under a nitrogen atmosphere and magnetic stirring at-78 ℃. After 3h reaction, tributyltin chloride (0.26g, 0.81mmol) was added rapidly. After 1 hour of reaction, the reaction was transferred to room temperature and reacted for 16 hours. After the reaction was quenched with 50mL of water, the organic phase was extracted three times (30mL of dichloromethane). All organic phases were freed of solvent by rotary removal under reduced pressure to give a yellow, viscous crude product. And (3) carrying out neutral alumina column chromatography separation on the crude product, drying the crude product by anhydrous magnesium sulfate, filtering the crude product, and removing the solvent by rotary removal under reduced pressure to obtain a product with the weight ratio of dichloromethane: petroleum ether at a volume ratio of 1:4 as eluent gave a yellow viscous solid (0.28g, yield 53%) which was used directly in the next reaction.
Example 3
D (A-Ar) based on carbazole eleven-membered condensed ring central nucleus2Target Compound of type TBTDBC (DPP)2、 TBTDBC(DPP-Cz)2、TBTDBC(DPP-Th)2And TBTDBC (DPP-ST)2The synthetic route of (A) is shown in the following formula.
Figure GDA0002694488270000171
Example 4
Target Compound TBTDBC (DPP)2And (4) synthesizing.
Figure GDA0002694488270000172
A100 mL dry three-necked flask was charged with the compound Br-DPP (185mg, 0.22mmol), 10mL toluene, and tetrakis (triphenylphosphine) palladium (Pd (PP)3)413mg,0.01mmol) and TBTDBC- [ Sn (CH)3)3]2(150mg,0.10 mmol). Stirring magnetically under the protection of nitrogen, heating to 110 ℃, and carrying out reflux reaction for 24 hours. The reaction was then cooled to room temperature, quenched with 5mL of water, and extracted three times with chloroform (20 mL). The organic phases are combined anddrying over magnesium sulfate, filtering and removing the solvent by rotary removal to obtain a black crude product. The crude product was immobilized on silica gel with a volume ratio of 1:3 of dichloromethane: petroleum ether is used as eluent to carry out column chromatography separation to obtain purple solid TBTDBC (DPP)2(150mg，yield 61％)。1H NMR(400MHz,CDCl3)(PPM):8.98(s,2H),8.86(s,2H),8.26(s,6H),7.97(s, 2H),7.80(s,2H),7.53(s,4H),7.44(s,2H),7.26(s,2H),7.16(s,2H),4.00(m,10H), 2.32(m,2H),1.91(m,4H),1.25(m,124H),0.83(m,33H).MALDI-MS(m/z)for C148H197N5O4S8:calcd.2364.31；found,2364.263for[M+].
Example 5
Target compound TBTDBC (DPP-Cz)2And (4) synthesizing.
Figure GDA0002694488270000181
A100 mL dry three-necked flask was charged with the compound Br-DPP-CZ (243mg,0.22 mmol), 10mL toluene, and tetrakis (triphenylphosphine) palladium (Pd (PP)3)4(13mg,0.01mmol) and TBTDBC- [ Sn (CH)3)3]2(150mg,0.10 mmol). Stirring magnetically under the protection of nitrogen, heating to 110 ℃, and carrying out reflux reaction for 24 hours. The reaction was then cooled to room temperature, quenched with 5mL of water, and extracted three times with chloroform (20 mL). The organic phases were combined, dried over anhydrous magnesium sulfate overnight, filtered and the solvent was removed by rotary evaporation to give a black crude product. The crude product was immobilized on silica gel with a volume ratio of 1:3 of dichloromethane: performing column chromatography separation with petroleum ether as eluent to obtain black solid TBTDBC (DPP-Cz)2(157mg,yield 52％)。1H NMR(400MHz,CDCl3)(ppm):9.05(s,4H),8.10(s,10H),7.87(s,4H), 7.52(s,10H),7.29(s,6H),7.16(s,2H),3.96(s,14H),2.06(s,2H),1.93(s,2H),1.44 (m,153H),0.88(m,36H).MALDI-MS(m/z)for C188H243N7O4S8:calcd. 2918.68；found,2922.048for[M+].
Example 6
Target compoundTBTDBC(DPP-Th)2And (4) synthesizing.
Figure GDA0002694488270000191
A100 mL dry three-necked flask was charged with the compound Br-DPP-Th (225mg, 0.22mmol), 10mL toluene, and tetrakis (triphenylphosphine) palladium (Pd (PP)3)413mg,0.01mmol) and TBTDBC- [ Sn (CH)3)3]2(150mg,0.10 mmol). Magnetically stirring under the protection of nitrogen, heating to 110 ℃, and carrying out reflux reaction for 24 hours. The reaction was then cooled to room temperature, quenched with 5mL of water, and extracted three times with chloroform (20 mL). Mixing organic phases, washing with 3 × 40mL saturated saline solution, drying the organic phase with anhydrous magnesium sulfate, filtering, removing solvent by spinning, separating the crude product by column chromatography with silica gel as stationary phase and dichloromethane and petroleum ether as eluent at a volume ratio of 1:3 to obtain black solid TBTDBC (DPP-Th)2(156mg，yield 55％)。1H NMR(400MHz,CDCl3)(ppm):8.91 (s,4H),8.18(s,4H),7.94(s,4H),7.52(s,4H),7.43(s,2H),7.26(s,4H),7.00(s,2H), 6.66(s,2H),4.01(m,10H),2.78(m,4H),1.93(m,4H),1.69(m,4H),1.28(m,150 H),0.86(m,36H).MALDI-MS(m/z)for C172H233N5O4S10:calcd.2752.54；found, 2753.060for[M+].
Example 7
Target compound TBTDBC (DPP-ST)2And (4) synthesizing.
Figure GDA0002694488270000192
A100 mL dry three-necked flask was charged with the compound Br-DPP-ST (232mg, 0.22mmol), 10mL toluene, and tetrakis (triphenylphosphine) palladium (Pd (PP)3)413mg,0.01mmol) and TBTDBC- [ Sn (CH)3)3]2(150mg,0.10 mmol). Magnetically stirring under the protection of nitrogen, heating to 110 ℃, and carrying out reflux reaction for 24 hours. The reaction was then cooled to room temperature and quenched with 5mL of waterAnd extracted three times with chloroform (20 mL). Mixing the organic phases, washing with 3 × 40mL saturated saline solution, drying the organic phase with anhydrous magnesium sulfate, filtering, removing the solvent by spinning, separating the crude product by column chromatography using silica gel as stationary phase and dichloromethane and petroleum ether as eluent in a volume ratio of 1:3 to obtain a black solid TBTDBC (DPP-ST)2(169mg，yield 58％)。1H NMR(400MHz,CDCl3)(ppm):8.85 (s,4H),8.29(s,2H),8.14(s,2H),7.90(s,4H),7.52(s,4H),7.33(s,4H),6.98(m, 6H),4.01(m,10H),2.88(m,4H),1.91(m,4H),1.76–1.66(m,4H),1.28(m,145H), 0.82(m,40H).MALDI-MS(m/z)for C172H233N5O4S12:calcd.2816.48；found, 2820.503for[M+].
Example 8
D(A-Ar)2The performance characterization of the small-molecule photovoltaic material and the manufacture and performance test of the photovoltaic device thereof. D (A-Ar)2Of small molecule photovoltaic materials1H NMR spectra were determined by a Bruker Dex-400 NMR instrument, mass spectra were determined using a Bruker Bifie MALDI TOF mass spectrometer and UV-visible absorption spectra were determined by a HP-8453 UV-visible spectrometer.
Based on D (A-Ar)nThe photovoltaic device of the small molecule material comprises: indium Tin Oxide (ITO) conductive glass anode layer, zinc oxide (ZnO) anode layer (30 nm). The active layer is formed by the small molecule material and PC71BM blending (20nm) with the blending ratio of 1:1.5, and the cathode made of MoO3(10nm)/Ag (100nm) layer.
The hole mobility of the device is Glass/ITO/PEDOT, PSS (10nm)/active layer (20 nm)/MoO3(10nm)/Au (100 nm).
Example 9
Small molecule TBTDBC (DPP)2Photophysical properties and photovoltaic device properties thereof
TBTDBC(DPP)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 2. Where the absorption spectra are approximately the same pattern but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. Calculating the optical band gap E of the material from the peak positiong optIs 1.80 eV.
TBTDBC(DPP)2The cyclic voltammogram in the solid film is shown in FIG. 4. It exhibits two sets of reversible oxidation peaks, which can be assigned to the donor and acceptor units, respectively. This gives the material a HOMO level and a LUMO level of-5.23 eV and-3.12 eV, respectively.
TBTDBC(DPP)2And PC71The J-V plot at a 1:1.5(w/w,20mg/mL) BM mixing ratio is shown in FIG. 5. Under this condition, the short-circuit current of the device was 5.76mA/cm2The open circuit voltage was 0.86V, the fill factor was 70.1%, and the photovoltaic efficiency was 3.47%.
TBTDBC(DPP)2And PC71The EQE curve at 1:1.5(w/w,20mg/mL) BM mix ratio is shown in FIG. 6. The graph shows the EQE test range of 300-750nm with a maximum EQE value at 480nm of 37%.
TBTDBC(DPP)2And PC71J of single electron device when the mixing ratio of BM is 1:1.5(w/w,20mg/mL)1/2the-V curve is shown in FIG. 7, and the hole mobility is at most 2.05X 10-4cm2V-1s-1。
Example 10
Micromolecule TBTDBC (DPP-Cz)2Photophysical properties and photovoltaic device properties thereof
TBTDBC(DPP-Cz)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 10. Where the absorption spectra are approximately the same pattern but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. Calculating the optical band gap E of the material from the peak positiong optIs 1.68 eV.
TBTDBC(DPP-Cz)2Cyclic voltammograms in solid films are shown in figure 11. It exhibits two sets of reversible oxidation peaks, which can be assigned to the donor and acceptor units, respectively. This gives the material a HOMO level and a LUMO level of-5.31 eV and-3.19 eV, respectively.
TBTDBC(DPP-Cz)2And PC71The J-V plot at a 1:1.5(w/w,20mg/mL) BM mixing ratio is shown in FIG. 12. Under the conditions of the reaction, the reaction solution is,the short-circuit current of the device is 5.31mA/cm2The open circuit voltage was 0.89V, the fill factor was 65.8%, and the photovoltaic efficiency was 3.11%.
TBTDBC(DPP-Cz)2And PC71The EQE curve at 1:1.5(w/w,20mg/mL) BM mix ratio is shown in FIG. 13. The graph shows the EQE test range of 300-750nm with a maximum EQE value of 35% at 480 nm.
TBTDBC(DPP-Cz)2And PC71J of single electron device when the mixing ratio of BM is 1:1.5(w/w,20mg/mL)1 /2the-V curve is shown in FIG. 14, and the hole mobility is at most 1.74X 10-4cm2V-1s-1。
Example 11
Small molecule TBTDBC (DPP-Th)2Photophysical properties and photovoltaic device properties thereof
TBTDBC(DPP-Th)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 17. Where the absorption spectra are approximately the same pattern but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. Calculating the optical band gap E of the material from the peak positiong optIt was 1.79 eV.
TBTDBC(DPP-Th)2Cyclic voltammograms in solid films are shown in figure 18. It exhibits two sets of reversible oxidation peaks, which can be assigned to the donor and acceptor units, respectively. This gives the material a HOMO level and a LUMO level of-5.20 eV and-3.39 eV, respectively.
TBTDBC(DPP-Th)2And PC71The J-V plot at a 1:1.5(w/w,20mg/mL) BM mixing ratio is shown in FIG. 19. Under this condition, the short-circuit current of the device was 4.51mA/cm2The open circuit voltage was 0.77V, the fill factor was 58.7%, and the photovoltaic efficiency was 2.04%.
TBTDBC(DPP-Th)2And PC71The EQE curve at 1:1.5(w/w,20mg/mL) BM mix ratio is shown in FIG. 20. The graph shows the EQE test range of 300-750nm with a maximum EQE value at 490nm of 27%.
TBTDBC(DPP-Th)2And PC71Mixing of BMJ of single electron device at ratio of 1:1.5(w/w,20mg/mL)1 /2the-V curve is shown in FIG. 21, and the hole mobility is at most 4.62X 10-5cm2V-1s-1。
Example 12
Micromolecule TBTDBC (DPP-ST)2Photophysical properties and photovoltaic device properties thereof
TBTDBC(DPP-ST)2The ultraviolet absorption spectrum in the solid film is shown in FIG. 24. Where the absorption spectra are approximately the same pattern but the absorption peaks are all red-shifted to different degrees due to pi-pi stacking in the solid film. Calculating the optical band gap E of the material from the peak positiong optIs 1.75 eV.
TBTDBC(DPP-ST)2Cyclic voltammograms in solid films are shown in figure 25. It exhibits two sets of reversible oxidation peaks, which can be assigned to the donor and acceptor units, respectively. This gives the material a HOMO level and a LUMO level of-5.24 eV and-3.44 eV, respectively.
TBTDBC(DPP-ST)2And PC71The J-V plot at a 1:1.5(w/w,20mg/mL) BM mixing ratio is shown in FIG. 26. Under this condition, the short-circuit current of the device was 5.25mA/cm2The open circuit voltage was 0.81V, the fill factor was 63.7%, and the photovoltaic efficiency was 2.71%.
TBTDBC(DPP-ST)2)2And PC71The EQE curve at 1:1.5(w/w,20mg/mL) BM mix ratio is shown in FIG. 27. The graph shows the EQE test range of 300-750nm with a maximum EQE value of 33% at 505 nm.
TBTDBC(DPP-ST)2And PC71J of single electron device when the mixing ratio of BM is 1:1.5(w/w,20mg/mL)1 /2the-V curve is shown in FIG. 28, and the hole mobility is at most 3.31X 10-5cm2V-1s-1。
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.

Claims (5)

1. D (A-Ar) based on carbazole eleven-membered condensed ring planar nucleus2A type organic photoelectric compound characterized in that: the D (A-Ar)2The organic photoelectric compound has one of the following structures:
Figure FDA0002732947470000011
Figure FDA0002732947470000021
。
2. the carbazole-undecene fused-ring planar core-based D (A-Ar) according to claim 12The preparation method of the organic photoelectric compound is characterized by comprising the following steps:
firstly, dissolving alkylated 2, 7-dibromo-3, 6-diiodo-carbazole in toluene, adding 2.0 mol of 2-trimethylstannylbenzene [ b ] thiophene with corresponding equivalent and 1-5% of tetrakis (triphenylphosphine) palladium into an inert gas environment, heating, refluxing, reacting overnight, extracting after the reaction is finished, drying, and purifying by column chromatography to obtain a product M2;
secondly, dissolving the product M2 in toluene, adding 2-3 molar equivalents of tin reagent and 1% -5% of tetrakis (triphenylphosphine) palladium, and heating and refluxing for 2-10 hours; after the reaction is finished, concentrating, extracting, drying and purifying by column chromatography to obtain a product M3;
thirdly, adding the product M3 into dichloromethane for dissolving, simultaneously adding 1-2 mL of nitromethane, selecting 275nm ultraviolet light for irradiating under the closed condition under the protection of inert gas for reacting for 5-8 hours at room temperature, adding a saturated ammonium chloride solution after the reaction is finished, extracting, drying, purifying by column chromatography, and recrystallizing to obtain a central nuclear product M4;
in the fourth step, the product M4 is addedDissolving in anhydrous tetrahydrofuran solution, cooling to-78 deg.C under the protection of inert gas, slowly dripping n-butyllithium solution into the solution, reacting for 3h, and adding SnBu3Adding Cl into the mixture quickly, continuing to react for 1h, transferring the reaction system to room temperature, and reacting for 16 h; quenching with water, extracting, removing solvent under reduced pressure to obtain yellow viscous crude product, separating by neutral alumina column chromatography, drying with anhydrous magnesium sulfate, filtering, removing solvent under reduced pressure, and eluting with dichloromethane and petroleum ether to obtain yellow viscous solid M5;
fifthly, dissolving a monomer Br-A-Ar in toluene under the protection of nitrogen, adding tetrakis (triphenylphosphine) palladium and an intermediate product M5, refluxing a reaction system for reaction overnight, then cooling, quenching with water, extracting, drying with anhydrous magnesium sulfate, filtering, and removing the solvent by rotary removal under reduced pressure to obtain a light yellow crude product, and performing column chromatography separation on the crude product by using dichloromethane and petroleum ether as an eluent to obtain yellow solid powder M6;
Figure FDA0002732947470000031
。
3. the carbazole deca-unitary fused-ring planar core-based D (A-Ar) of claim 12The application of the organic photoelectric compound is characterized in that: the prepared carbazole multi-fused ring derivative has high hole mobility, and can be used as an active layer to be applied to organic solar cells, organic field effect transistors, organic electroluminescent diodes and organic near infrared photoelectric detectors.
4. D (A-Ar) according to claim 32The application of the organic photoelectric compound is characterized in that: the thickness of the active layer is between 20 nanometers and 1000 nanometers.
5. D (A-Ar) according to claim 32The application of the organic photoelectric compound is characterized in that: the active layer is realized by a solution processing method, including spin coating and brushingCoating, spraying, dipping, roll coating, screen printing or ink jet printing methods; wherein the solvent is organic solvent.
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