CN109970768A - Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and preparation method and application - Google Patents

Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and preparation method and application Download PDF

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CN109970768A
CN109970768A CN201910284775.9A CN201910284775A CN109970768A CN 109970768 A CN109970768 A CN 109970768A CN 201910284775 A CN201910284775 A CN 201910284775A CN 109970768 A CN109970768 A CN 109970768A
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carbazole
dpp
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CN109970768B (en
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刘煜
高辉山
刘座吉
朱卫国
杨振
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Changzhou University
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Abstract

D (A-Ar) the present invention relates to one kind based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric compound and its preparation method and application.Ternary carbazole center ring element is passed through into coupling thiophene and benzothiophene derivative, by ring closure reaction and coupling reaction, the derivative of ten unitary condensed ring conjugate planes structure aromatic compounds of a kind of carbazolyl-containing and the D (A-Ar) of the polynary condensed ring centronucleus containing carbazole are obtained2Linear small organic molecule photovoltaic material.Derivative D (A-Ar) corresponding with its of such big condensed ring conjugate planes structural compounds of ten unitary2Linear small organic molecule photovoltaic material has high thermal stability and high hole mobility.By the exploitation and application of such material, efficient organic solar batteries, organic electroluminescent LED, organic field effect tube and organic near infrared photodetector material are obtained.

Description

Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and system Preparation Method and application
Technical field
It include ten unitary condensed ring plane kernel D (A-Ar) of carbazole present invention relates particularly to molecular backbone donor core2Linear is small Molecular material can be applied to organic photoelectric technical field.
Background technique
Organic solar batteries have become photovoltaic art research hotspot because of the advantages that its is inexpensive, light and large area prepares.
The small organic molecule donor material in the photosensitive activity layer of electric energy is converted to as sunlight is absorbed, due to pure Abbreviation list, specific structure, is easy to outstanding advantages of modification and good batch reproducibility at monodispersity, has biggish city Field application prospect.Therefore, organic solar batteries cause more and more concerns.
Currently based on organic molecule solar cell material still have absorption spectrum is narrow, carrier mobility is low, effect The problem in science such as rate is not high and stability is poor, need the high-performance small molecule donor material of Development of Novel.
Summary of the invention
Present invention aims at described based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound Derivative is obtained by cyclization and coupling reaction.A kind of preferable coplanarity, wide UV absorption and high mobility are provided Based on ten unitary condensed ring conjugate planes core of carbazole and its D (A-Ar)2Type derivant structure small molecule material and its in organic photoelectric Application in device.Such small molecule material have specific molecular structure, be easy to modify and batch it is reproducible, good point The charge-trapping energy of organic battery device can be improved in the features such as sub- flatness, wider UV absorption and higher mobility Power, short circuit current, fill factor have important potentiality in terms of the energy conversion efficiency for improving battery device.
It is of the present invention to be based on ten unitary condensed ring conjugate planes core of carbazole and its D (A-Ar)2Type derivative, it is main special Point is: being donor core (D) based on ten unitary condensed ring conjugate planes center of carbazole, the conjugated structure with electron withdrawing properties is A Unit and end condensed-nuclei aromatics unit Ar, construct D (A-Ar) by even chain reaction2Linear small organic molecule derivative donor material Material.
Technical solution of the present invention is as follows:
Containing ten unitary condensed ring conjugate planes donor core of carbazole and its D (A-Ar)2Linear small molecule has a flowering structure:
Wherein, R is independently selected from C16~C20Branched alkyl；
Wherein, D is based on ten unitary condensed ring conjugate planes centronucleus of carbazole, X S, O or Se atom；
Wherein, A is the conjugate unit with electron withdrawing properties, and the A conjugate unit is thiophene pyrrole and pyrroledione, thiophene Azoles pyrrolo-pyrrole-dione, phenylpyrrole and pyrroledione, pyridazole and pyrroledione, bioxindol, pyridine bioxindol, thiophene Bioxindol, double thiophene [3,4-b] pyrroledione, acid imide, naphthalimide, thiophene [4,5-b] and pyridone, double fluoro- thiophene [4,5-b] and pyridone, single fluorine diazosulfide, double fluorine diazosulfides, monochloro diazosulfide, double chlorine diazosulfides, It is alkoxy diazosulfide, pyrydinothiadiazole, single fluorine selenole, double fluorine selenoles, monochloro selenole, double Chlorine selenole, alkoxy selenole, pyrido selenium diazole, thiophene [3,4-b] simultaneously the fluoro- thiophene ester of -3-, thiophene [3, 4-b] simultaneously simultaneously simultaneously the chloro- thienone of -3-, benzo are double for the fluoro- thienone of -3-, thiophene [3,4-b] for the chloro- thiophene ester of -3-, thiophene [3,4-b] It is thiadiazoles, benzene [2,3-c] pyrroledione, thiophene [2,3-c] pyrroledione, benzene thiophene diketone, double fluorine benzotriazole, double Chloro-Benzotriazole, one of fluorination, chlorination and the above substance of alkoxylated quinoxaline or one of its derivative；
Further, the A conjugate unit one of has the following structure:
Further, conjugation receptor unit A can be modified by alkyl chain, R1Independently selected from C6~C12Linear chain or branched chain alkane Base.
Wherein, Ar is that the end of hydrogen atom, fluorine atom or functionalization is conjugated donor monomer.The Ar conjugate unit is dioxane The fluoro- 2- alkylthrophene of base thiophene, 4-, the fluoro- 2- alkylthrophene of 3,4- bis-, 2- alkyl thiol-thiophene, 2- alkyl thiazole, 2- alkyl The chloro- 2- alkylthrophene of thyroidan, 4-, 2- tin alkyl pheno, 2- alkyl thiol selenophen, 2- alkyl selenazoles, 2- alkyl thiol selenazoles, 4- fluorobenzene, 2,4 difluorobenzene, 4- alkylbenzene, 4- alkoxy benzene, benzo [b] thiophene, benzo [b] furans, benzo [b] selenazoles, benzene And [b] tellurium azoles, alkylthrophene simultaneously [3,2-b] thiophene, alkyl thiol thieno [3,2-b] thiophene, 2- or 3-9- alkyl carbazole, 2- Or 3-9,9- dialkyl fluorene, triaryl amine, 2- naphthalene, 2- anthracene, 2- be luxuriant and rich with fragrance or 2- pyrene；
Further, Ar is that the end of functionalization is conjugated donor monomer, and Ar can be modified by alkyl chain, R1Independently selected from C6 ~C12One of linear or branched alkyl group, have the following structure:
Further, D is to be had the following structure based on ten unitary condensed ring conjugate planes centronucleus donor monomer of carbazole It is a kind of:
D (A-Ar) based on ten unitary condensed ring planar central core of carbazole2Type organic photoelectric compound is as active layer material Applied in organic photovoltaic devices.
Compared with the prior art, the present invention has the following advantages:
1) D (A-Ar) based on ten unitary condensed ring conjugate planes centronucleus of carbazole synthesized by the present invention2Type is conjugated small point Son has the characteristics that structure is clear, molecular weight is determining, batch repeatability is high, and such small molecule material can use chloroform, tetrahydro furan It mutters, the dissolution of chlorobenzene, o-dichlorohenzene equal solvent, as active layer solution processable, is produced in the following organic photovoltaic devices large area Aspect tool has great advantage.
2) D (A-Ar) based on ten unitary condensed ring conjugate planes centronucleus of carbazole synthesized by the present invention2Type is conjugated small point There is son excellent plane performance, good charge to extract performance, wider UV absorption, good molar absorption coefficient, can be with Improve fill factor, short circuit current and the energy conversion efficiency of battery device.
3) D (A-Ar) based on ten unitary condensed ring conjugate planes centronucleus of carbazole synthesized by the present invention2Type is conjugated small point Son shows some superiority in terms of production thick film boundary material and device, has very in the production of the following organic photovoltaic cell large area Big potentiality.
4) material of the present invention is at classical D (A-Ar)2In structure basis, there is hole transport performance by introducing The condensed-nuclei aromatics D unit of carbazole planar structure, it is intended to realize narrow band gap, the response of wide spectrum band and high mobility organic photovoltaic donor The macromolecular architecture of material and its application in solvent processing type body heterojunction organic solar batteries.This kind of D (A-Ar)nType The molecular structure of structural material can be any one of following molecule.
The above-mentioned D (A-Ar) based on ten unitary condensed ring conjugate planes centronucleus of carbazole2Linear small organic molecule photovoltaic material Material, including following any derivative:
Using ten unitary condensed ring conjugate planes centronucleus of carbazole as donor monomer (D), Diketopyrrolopyrrolederivative derivative is to draw Electron group (A), end (Ar) are the D- (A-Ar) of H atom2Linear small molecule photovoltaic material TBTDBC (DPP)2。
Using ten unitary condensed ring conjugate planes centronucleus of carbazole as donor monomer (D), Diketopyrrolopyrrolederivative derivative is to draw Electron group (A), end (Ar) are the D- (A-Ar) of 3- -9- octylcarbazols2Linear small molecule photovoltaic material TBTDBC (DPP-Cz)2。
Using ten unitary condensed ring conjugate planes centronucleus of carbazole as donor monomer (D), Diketopyrrolopyrrolederivative derivative is to draw electricity Subbase group (A), end (Ar) are the D- (A-Ar) of 5- octyl thiophene2Linear small molecule photovoltaic material TBTDBC (DPP-Th)2。
Using ten unitary condensed ring conjugate planes centronucleus of carbazole as donor monomer (D), Diketopyrrolopyrrolederivative derivative is to draw Electron group (A), end (Ar) are the D- (A-Ar) of the pungent mercapto-thiophene of 5-2Linear small molecule photovoltaic material TBTDBC (DPP- ST)2。
The preparation method of above-mentioned material in order to obtain, material of the present invention is as follows:
The D (A-Ar)2Type molecule photovoltaic material planar central core (D) is i.e. based in ten unitary condensed ring conjugate planes of carbazole The synthesis (main point or less three steps carry out) of heart core TBTDBC:
1) first step, alkylated 2,7-, the bis- iodo- carbazole of bromo- 3,6- bis- are dissolved in toluene, are added in inert gas environment Enter 2- tin trimethyl benzene [b] thiophene of 2.0 moles of corresponding equivalents, 1%~5% four (triphenylphosphines) close palladium, are heated to reflux anti- It should stay overnight, after reaction, extract, dry, column Chromatographic purification obtains intermediate 3, bis- (benzothiophene-2- bases)-2,7-two of 6- Bromo- 9- (2- octyldodecyl) -9- carbazole.
2) second step, by intermediate 3, bis- (benzothiophene-2- bases)-2 of 6-, 7-two bromo- 9- (2- octyldodecyl)-9- Carbazole is dissolved in toluene, and the 2- tin trimethyl thiophene of 2~3 molar equivalents is added, and 1%~5% four (triphenylphosphines) close palladium, Heating reflux reaction 2~10 hours.After reaction, it is concentrated, extracts, dry, column Chromatographic purification obtains intermediate product 3, and 6- is bis- (benzothiophene -2- base) -9- (2-- octyldodecyl) -2,7- two (thiophene -2- base) -9- carbazole.
3) third step, by intermediate product 3, bis- (thiophene of 6- bis- (benzothiophene -2- bases) -9- (2- octyldodecyl) -2,7- Pheno -2- base) dissolution of -9- carbazole adding into dichloromethane, while the nitromethane of 1~2mL is added, it is close under inert gas shielding It under the conditions of closing, selects in room temperature reaction 5~8 hours under 275nm ultraviolet light, it is molten that saturated ammonium chloride is added after reaction Liquid, extraction, drying, column Chromatographic purification, recrystallization, obtains center donor core TBTDBC.
The tin reagentization of the material center core TBTDBC prepares TBTDBC- [Sn (CH3)3]2:
It will obtain center donor core TBTDBC and be added in anhydrous tetrahydrofuran solution to dissolve, it is cooling under inert gas shielding - 78 degrees Celsius are caused, n-BuLi (0.97mL, 1.55mmol, 1.6M) solution is slowly added dropwise into wherein, 3h is reacted, it will SnBu3Cl is rapidly added wherein, after the reaction was continued 1h, reaction system is transferred at room temperature, 16h is reacted.It is quenched with water Afterwards, it extracts.Decompression rotation obtains the crude product of yellow, viscous except solvent.Crude product is through neutral alumina column chromatography for separation, anhydrous sulphur Sour magnesium is dry, filtering, depressurizes rotation except solvent, and finally using methylene chloride: petroleum ether obtains the sticky shape of yellow of tin agent as eluant, eluent Solid TBTDBC- [Sn (CH3)3]2。
The D (A-Ar)2The synthesis of Linear molecule photovoltaic material side chain receptor A:
D(A-Ar)2Linear small molecule photovoltaic material side chain Br-DPP synthesis: directly buying has from the resistance to Jilin Chemical of Town in Shanghai Limit company.
D(A-Ar)2Linear small molecule photovoltaic material side chain Br-DPP-Cz synthesis: it in toluene solvant, sequentially adds Wet chemical and 9- octyl -3- (penta ring -2- base of 4,4,5,5- tetramethyl -1,3,2- dioxy boron)-click of Br-DPP, 2M Azoles obtains DPP-Cz violet solid through column chromatography for separation by suzuki coupling reaction under nitrogen protection；In dark ambient conditions Under ice bath, the NBS of DPP-Cz violet solid and corresponding amount is sequentially added, by reaction 6 hours, obtains purple through column chromatography for separation Color solid Br-DPP-Cz.
D(A-Ar)2Linear small molecule photovoltaic material side chain Br-DPP-Th synthesis: it in toluene solvant, sequentially adds The wet chemical and 5- octyl -2- tributyl first tinbase thiophene of Br-DPP, 2M are coupled by stille under nitrogen protection anti- It answers, obtains the side chain DPP-Th violet solid of target molecule through column chromatography for separation；Under dark ambient conditions and ice bath, successively plus The NBS for entering DPP-Th violet solid and corresponding amount obtains atropurpureus solid Br- through column chromatography for separation by reaction 6 hours DPP-Th。
D(A-Ar)2Linear small molecule photovoltaic material side chain Br-DPP-ST synthesis: it in toluene solvant, sequentially adds The wet chemical and 5- of Br-DPP, 2M pungent sulfydryl -2- tributyl first tinbase thiophene pass through stille under nitrogen protection and are coupled Reaction, obtains the side chain DPP-ST violet solid of target molecule through column chromatography for separation；Under dark ambient conditions and ice bath, successively The NBS of DPP-ST violet solid and corresponding amount is added, by reaction 6 hours, obtains atropurpureus solid Br- through column chromatography for separation DPP-ST。
D(A-Ar)2Type small molecule photovoltaic material object molecule TBTDBC (DPP)2Synthesis: in toluene solvant, successively plus Enter side chain Br-DPP and centronucleus tin reagent TBTDBC- [Sn (CH3)3]2, nitrogen protection simultaneously tetra-triphenylphosphine palladium catalysis issue Raw stille coupling reaction, synthesis obtain D (A-Ar)2Linear small molecule photovoltaic material object compound TBTDBC (DPP)2, slightly Product obtains sterling through column chromatography for separation.
D(A-Ar)2Type small molecule photovoltaic material object molecule TBTDBC (DPP-Cz)2Synthesis: in toluene solvant, according to Secondary addition side chain Br-DPP-Cz and centronucleus tin reagent TBTDBC- [Sn (CH3)3]2, nitrogen protection simultaneously urges in tetra-triphenylphosphine palladium Change lower generation stille coupling reaction, synthesis obtains D (A-Ar)2Linear small molecule photovoltaic material object compound TBTDBC (DPP-Cz)2, crude product obtains sterling through column chromatography for separation.
D(A-Ar)2Type small molecule photovoltaic material object molecule TBTDBC (DPP-Th)2Synthesis: in toluene solvant, according to Secondary addition side chain Br-DPP-Th and centronucleus tin reagent TBTDBC- [Sn (CH3)3]2, nitrogen protection simultaneously urges in tetra-triphenylphosphine palladium Change lower generation stille coupling reaction, synthesis obtains D (A-Ar)2Linear small molecule photovoltaic material object compound TBTDBC (DPP-Th)2, crude product obtains sterling through column chromatography for separation.
D(A-Ar)2Type small molecule photovoltaic material object molecule TBTDBC (DPP-Cz)2Synthesis: in toluene solvant, according to Secondary addition side chain Br-DPP-ST and centronucleus tin reagent TBTDBC- [Sn (CH3)3]2, nitrogen protection simultaneously urges in tetra-triphenylphosphine palladium Change lower generation stille coupling reaction, synthesis obtains D (A-Ar)2Linear small molecule photovoltaic material object compound TBTDBC (DPP-ST)2, crude product obtains sterling through column chromatography for separation.
D (A-Ar) of the invention2Type small molecule photovoltaic material compared with published most of small molecule photovoltaic materials, Feature is: (1) due to the molecular structure of plane, the D (A-Ar) of designnType small molecule material has better filming performance； (2) due to be conjugated the big flat unit TBTDBC in center introducing, small molecule material have narrower band gap, band response also compared with It is wide；(3) target small molecule has stronger intermolecular pi-pi accumulation effect；(4) in molecule push-pull configuration presence, target small molecule Delocalization degree it is high, the charge transport ability of intermolecular active force and molecule can be enhanced, be conducive to the transmission of device electronic. Therefore, this kind of material is a kind of very promising small organic molecule photovoltaic material.
Application of the invention is: using the design synthesis photovoltaic material as donor, with PC71BM in the case where not arranging on year-on-year basis It is blended, makes photovoltaic device, realize and solar energy is preferably converted into electric energy.
The small organic molecule photovoltaic material has made body heterojunction organic solar batteries device, device architecture For Glass/ITO/ZnO (30nm)/Compounds:PC71BM(20nm)/MoO3(10nm)/Ag(100 nm).Including tin oxide Indium Conducting Glass layer (ITO), ZnO anode layer.Wherein anode modification layer is poly- ethylenedioxythiophene (PEDOT, 30nm) painting Layer；Cathode is MoO3The sedimentary of (10nm)/Ag (100nm)；Activation layer material is D of the present invention (A-Ar)nMolecule with PC71BM, blending weight ratio are 1:1.5 (w/w, 20mg/mL).
Hole mobility device architecture be Glass/ITO/PEDOT:PSS (10nm)/active layer (20 nm)/ MoO3It is tested under (10nm)/Au (100nm).
Detailed description of the invention
Fig. 1 is TBTDBC of the present invention (DPP)2Thermogravimetric curve figure
Fig. 2 is TBTDBC of the present invention (DPP)2UV-visible absorption spectrum in dichloromethane solution
Fig. 3 is TBTDBC of the present invention (DPP)2UV-visible absorption spectrum in solid film
Fig. 4 is TBTDBC of the present invention (DPP)2Cyclic voltammetry curve figure on solid film
Fig. 5 is TBTDBC of the present invention (DPP)2With PC71The mixed proportion of BM is the J-V under 1:1.5 (w/w, 20 mg/mL) Curve graph
Fig. 6 is TBTDBC of the present invention (DPP)2With PC71The mixed proportion of BM is that EQE is bent under 1:1.5 (w/w, 20 mg/mL) Line chart
Fig. 7 is TBTDBC of the present invention (DPP)2With PC71The J-V performance diagram of the blend film list hole device of BM
Fig. 8 is TBTDBC of the present invention (DPP-Cz)2Thermogravimetric curve figure
Fig. 9 is TBTDBC of the present invention (DPP-Cz)2UV-visible absorption spectrum in dichloromethane solution
Figure 10 is TBTDBC of the present invention (DPP-Cz)2UV-visible absorption spectrum in solid film
Figure 11 is TBTDBC of the present invention (DPP-Cz)2Cyclic voltammetry curve figure on solid film
Figure 12 is TBTDBC of the present invention (DPP-Cz)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) J-V curve graph
Figure 13 is TBTDBC of the present invention (DPP-Cz)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) EQE curve graph
Figure 14 is TBTDBC of the present invention (DPP-Cz)2With PC71The J-V performance diagram of the blend film list hole device of BM
Figure 15 is TBTDBC of the present invention (DPP-Th)2Thermogravimetric curve figure
Figure 16 is TBTDBC of the present invention (DPP-Th)2UV-visible absorption spectrum in dichloromethane solution
Figure 17 is TBTDBC of the present invention (DPP-Th)2UV-visible absorption spectrum in solid film
Figure 18 is TBTDBC of the present invention (DPP-Th)2Cyclic voltammetry curve figure on solid film
Figure 19 is TBTDBC of the present invention (DPP-Th)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) J-V curve graph
Figure 20 is TBTDBC of the present invention (DPP-Th)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) EQE curve graph
Figure 21 is TBTDBC of the present invention (DPP-Th)2With PC71The J-V performance diagram of the blend film list hole device of BM
Figure 22 is TBTDBC of the present invention (DPP-ST)2Thermogravimetric curve figure
Figure 23 is TBTDBC of the present invention (DPP-ST)2UV-visible absorption spectrum in dichloromethane solution
Figure 24 is TBTDBC of the present invention (DPP-ST)2UV-visible absorption spectrum in solid film
Figure 25 is TBTDBC of the present invention (DPP-ST)2Cyclic voltammetry curve figure on solid film
Figure 26 is TBTDBC of the present invention (DPP-ST)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) J-V curve graph
Figure 27 is TBTDBC of the present invention (DPP-ST)2With PC71The mixed proportion of BM is under 1:1.5 (w/w, 20 mg/mL) EQE curve graph
Figure 28 is TBTDBC of the present invention (DPP-ST)2With PC71The J-V performance diagram of the blend film list hole device of BM
Figure 29 is TBTDBC of the present invention (DPP)2Mass spectrogram
Figure 30 is TBTDBC of the present invention (DPP-Cz)2Mass spectrogram
Figure 31 is TBTDBC of the present invention (DPP-Th)2Mass spectrogram
Figure 32 is TBTDBC of the present invention (DPP-ST)2Mass spectrogram
Specific embodiment
Below by specific embodiment, the invention will be further described, but these specific embodiments are not in any way It limits the scope of the invention.
Embodiment 1
D (A-Ar) based on ten unitary condensed ring centronucleus of carbazole2The intermediate of the linear small molecule of type organic photoelectric compound (DPP-Cz, Br-DPP-Cz, DPP-Th, Br-DPP-Th, DPP-ST, Br-DPP-ST) synthetic route is as shown below.
1.1,2,5- it is bis--(ten alkyl of 2- hexyl) -3- (5- (9- octylcarbazol -3- base) thiophene -2- base) -6- (thiophene -2- Base) pyrrolo- [3,4-c] pyrroles -1,4- diketone (DPP-Cz) synthesis
2,5- bis- (2- hexyl decyl) -3- (5- bromothiophene -2- base) -6- is sequentially added in 100mL dry there-necked flask In (thiophene -2- base) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone (Br-DPP) (0.50g, 0.60mmol), 30mL toluene, four (triphenylphosphine) palladium (Pd (PP3)4, 35mg, 0.03mmol), 9- octyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxy boron penta Ring -2- base)-carbazole (267mg, 0.66mmol), solution of potassium carbonate (2M, 3mL) and Aliquant 336 (4 drop).Back flow reaction For 24 hours, cooling, with 3 × 25mL chloroform extraction, merge organic phase, then with 3 × 40mL saturated common salt water washing, anhydrous slufuric acid Magnesium dries organic phase, filtering, and rotation removes solvent, and crude product uses silica gel as stationary phase, the methylene chloride for being 1:4 with volume ratio: stone Oily ether is that eluant, eluent carries out column chromatography for separation.Obtain violet solid (334mg, yield 54%).1H NMR (400MHz, CDCl3) δ (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).
1.2,3- (5- bromothiophene -2- base) -2,5- couples-(ten alkyl of 2- hexyl) -3-6- (5- (9- octyl-carbazole -3- base) - 2 base of thiophene)-pyrrolo- [3,4-c] pyrroles -1,4- diketone (Br-DPP-Cz) synthesis
Compound DPP-CZ (334mg, 0.33mmol) and 20mL trichlorine are sequentially added in 100mL dry there-necked flask Methane, ice bath and in a dark environment magnetic agitation, slowly from constant pressure funnel be added dropwise dissolved with NBS (59mg, Chloroform soln 0.33mmol).After being added dropwise, reaction system is quenched with 20mL water after reacting 6h, with 3 × 25mL chloroform extraction.Anhydrous magnesium sulfate dries organic phase, filtering, and rotation removes solvent, and crude product is used silica gel as stationary phase, used Volume ratio is the methane of 1:3: petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains violet solid (335mg, yield 93%).1H NMR(400 MHz,CDCl3) δ (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).
1.3,2,5- it is bis--(ten alkyl of 2- hexyl) -3- [5-9- octyl-(2,2- Dithiophene) -5- base] -6 (thiophene -2- bases) The synthesis of pyrrolo- [3,4-c] pyrroles -1,4- diketone (DPP-Th)
2,5- bis- (2- hexyl decyl) -3- (5- bromothiophene -2- base) -6- is sequentially added in 100mL dry there-necked flask (thiophene -2- base) pyrrolo- [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone Br-DPP (0.50g, 0.60mmol), 30mL toluene, four (triphens Base phosphine) palladium (Pd (PP3)4, 35mg, 0.03mmol) and 5- octyl -2- tributylStannylThiophene (321mg, 0.66mmol). It is warming up to 110 DEG C under nitrogen protection, reaction system is cooled to room temperature by back flow reaction afterwards for 24 hours.Reaction system is dilute with 10mL After hydrochloric acid, (20mL chloroform) reaction system is extracted in three times.Merge organic phase, then with 3 × 40mL saturated salt solution Washing, the dry organic phase of anhydrous magnesium sulfate, filtering, decompression rotation remove solvent, and crude product uses silica gel as stationary phase, is with volume ratio The methylene chloride of 1:4: petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains violet solid (420mg, yield 74%).1H NMR(400MHz,CDCl3) δ (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)
1.4,3- (5- bromothiophene -2- base) -2,5- couples-(ten alkyl of 2- hexyl) -6- (5- (octyl)-[2,2- Dithiophene] - 5- yl) pyrrolo- [3,4-c] pyrroles -1,4- diketone (Br-DPP-Th) synthesis
Compound DPP-Th (420mg, 0.45mmol) and 20mL trichlorine are sequentially added in 100mL dry there-necked flask Under condition of ice bath, in dark surrounds, the trichlorine dissolved with NBS (80mg, 0.45mmol) is slowly added dropwise in methane, magnetic agitation Dichloromethane.After being added dropwise, reaction system is gone out after reacting 6h with 20 mL water quenchings, extracts (20mL chloroform) in three times Reaction system.Merge organic phase, then use 3 × 40 mL saturated common salt water washings, the dry organic phase of anhydrous magnesium sulfate, filtering is depressurized Rotation removes solvent, and crude product uses silica gel as stationary phase, and the methylene chloride for being 1:3 with volume ratio: petroleum ether is that eluant, eluent carries out column Chromatography obtains violet solid (432mg, yield 95%).1H NMR(400MHz,CDCl3) δ (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).
1.5,2,5- it is bis--(ten alkyl of 2- hexyl) -3- [5- (pungent sulfydryl)-(2,2- Dithiophene) -5- base] -6 (thiophene -2- Base) pyrrolo- [3,4-c] pyrroles -1,4- diketone (DPP-ST) synthesis
(2- hexyl the decyl) -3- of compound 2,5- bis- (5- bromothiophene -2- is sequentially added in 100mL dry there-necked flask Base) -6- (thiophene -2- base) pyrrolo- [3,4-c] pyrroles's-Isosorbide-5-Nitrae-diketone Br-DPP (0.50g, 0.60 mmol), 30mL toluene, Tetrakis triphenylphosphine palladium (Pd (PP3)4, 35mg, 0.03mmol) and the pungent sulfydryl -2- tributylstamlyl thiophene of 5- (342mg, 0.66mmol).It is warming up to 110 DEG C under nitrogen protection, reaction system is cooled to room temperature by back flow reaction afterwards for 24 hours.By reactant After system is quenched with 10mL dilute hydrochloric acid, (20mL chloroform) reaction system is extracted in three times.Merge organic phase, then with 3 × 40mL Saturated common salt water washing, the dry organic phase of anhydrous magnesium sulfate, filtering, decompression rotation remove solvent, and crude product uses silica gel as stationary phase, The methylene chloride for being 1:4 with volume ratio: petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains violet solid 410mg, yield 70%).1H NMR(400MHz,CDCl3) δ (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).
1.6,3- (5- bromothiophene -2- base) -2,5- couples-(ten alkyl of 2- hexyl) -6- (5- (pungent sulfydryl)-[bis- thiophene of 2,2- Pheno] -5- base) pyrrolo- [3,4-c] pyrroles -1,4- diketone (Br-DPP-ST) synthesis
Compound DPP-ST (410mg, 0.42mmol) and 20mL trichlorine are sequentially added in 100mL dry there-necked flask In methane, under condition of ice bath, in dark surrounds, three dissolved with NBS (75mg, 0.42mmol) are slowly added dropwise in magnetic agitation Chloromethanes solution.After being added dropwise, reaction system is quenched after reacting 6h with 20mL water, extracts (20mL trichlorine in three times Methane) reaction system.Merging organic phase, then uses 3 × 40mL saturated common salt water washing, the dry organic phase of anhydrous magnesium sulfate filters, Decompression rotation removes solvent, and crude product uses silica gel as stationary phase, the methylene chloride for being 1:3 with volume ratio: petroleum ether for eluant, eluent into Row column chromatography for separation obtains violet solid (426mg, yield 96%).1H NMR(400MHz,CDCl3)δ(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).
Embodiment 2
Based on D (A-Ar)2The ten unitary condensed ring centronucleus tin reagent TBTDBC- [Sn of carbazole of type organic photoelectric compound (CH3)3]2Synthetic route it is as shown below.
2.1, the synthesis of bis- bromo- 3,6- bis- iodo- 9- (2- octyldodecyl) carbazole (M1) of 2,7-
In 100mL there-necked flask, 2,7-, bis- bromo- carbazole (3g, 4.97mmol) and 50mL acetic acid are sequentially added, logical nitrogen deoxidation is set It changes three times, magnetic agitation, dissolves reactant at 80 DEG C, quickly weigh potassium iodide (2.22 g, 13.41mmol) and periodic acid Potassium (1.43g, 6.71mmol), and be added sequentially in reaction system, back flow reaction 12h.It is cooled to room temperature after fully reacting, it will Mixed liquor is poured into 100mL water and is quenched, and is washed with chloroform extraction (100mL × 3) and saturated sodium bisulfite solution (100mL×3).Merge organic phase and with anhydrous MgSO4It is dried overnight, filters, depressurizing rotation except solvent, obtaining the thick production of grey Product.Crude product after concentration is that eluant, eluent carries out silica gel column chromatography separation with petroleum ether (PE), obtain white solid (3.5g, Yield 83%).1H NMR(CDCl3, 400MHz), δ (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, the conjunction of bromo- 9- (2- the octyldodecyl)-9- carbazole (M2) of 3,6- bis- (benzothiophene-2- bases)-2,7-two At
Compound M1 (3g, 3.5mmol) is dissolved in 60mL toluene, tetrakis triphenylphosphine palladium (Pd (PP is added3)4, 202mg, 0.18mmol).2- tributyl-methyl phosphonium tin benzothiophene is slowly added dropwise at 80 DEG C in magnetic agitation under nitrogen protection (3.0g, 7.0mmol).After being added dropwise, 110 DEG C are warming up to, back flow reaction for 24 hours, cools down reaction solution.It is quenched with 100mL dilute hydrochloric acid After going out, reaction system (30 mL methylene chloride) is extracted in three times.Anhydrous magnesium sulfate dries, filters, and decompression rotation removes solvent, obtains Lurid crude product.Crude product carries out column chromatography for separation, and using methylene chloride: the volume ratio of petroleum ether is 1:20 as eluant, eluent. Finally obtain light yellow sticky shape solid (1.28g, yield 42%).1H NMR(400MHz,CDCl3)δ(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).
2.3,9- (2- octyldodecyl) -2,7- two (thiophene -2- base) -3,6- two (benzothiophene -2- base) carbazole (M3) synthesis
Compound M2 (1g, 1.2mmol) is dissolved in 40mL toluene, tetrakis triphenylphosphine palladium (Pd is sequentially added (PP3)4, 67mg, 0.06mmol) and 2- tributylstamlyl thiophene (0.99g, 2.64mmol).It is heated under nitrogen protection 110 DEG C, reaction system is slowly cooled down after back flow reaction 36h.After being quenched with 40mL dilute hydrochloric acid, reaction system is extracted in three times (30mL methylene chloride).Anhydrous magnesium sulfate dries, filters, and decompression rotation removes solvent, obtains lurid crude product.Crude product carries out Column chromatography for separation, using methylene chloride: the volume ratio 1:6 of petroleum ether is eluant, eluent.Obtain the sticky shape solid of yellow (0.72g, Yield 72%).1H NMR(400 MHz,CDCl3) δ (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, the synthesis of planar central core TBTDBC
Compound M3 (0.70g, 0.80mmol) is dissolved in the dry methylene chloride of 60mL, it under nitrogen protection, will Reaction system is placed in ice bath, magnetic agitation 10min.The anhydrous ferric trichloride in the dry nitromethane of 1.0mL will be dissolved in (0.90g, 5.6mmol), is slowly added dropwise in reaction system, under 375 nm ultraviolet lights, reacts at room temperature 5~8 hours, then 40mL anhydrous methanol is added to reaction system, reacts 30min.Reaction mixture is washed with saturated ammonium chloride solution (30mL), is used Methylene chloride extracts (30mL) three times.Anhydrous magnesium sulfate dries, filters, and decompression rotation removes solvent, obtains the crude product of yellow.Slightly Product carries out column chromatography for separation, and the ratio of the eluant, eluent used is methylene chloride: petroleum ether 1:4.Finally obtain yellow solid (0.56g, yield 80%).1H NMR(400MHz,CDCl3)δ(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, the tinbase compound TBTDBC- [Sn (CH of centronucleus3)3]2Synthesis
Compound TBTDBC (0.32g, 0.37mmol) is dissolved in the dry tetrahydrofuran of 50mL, nitrogen atmosphere, Under the conditions of -78 DEG C, n-BuLi (0.97mL, 1.55mmol, 1.6M) solution is slowly added dropwise into wherein for magnetic agitation.Reaction Tributyltin chloride (0.26g, 0.81mmol) is then rapidly added wherein by 3h.After reacting 1h, reaction system is transferred to room Under temperature, 16h is reacted.After reaction system is quenched with 50mL water, organic phase (30mL methylene chloride) is extracted in three times. The decompression rotation of all organic phases is removed into solvent, obtains the crude product of yellow, viscous.Crude product carries out neutral alumina column chromatography Separation, anhydrous magnesium sulfate dry, filter, and decompression rotation removes solvent, and using methylene chloride: the volume ratio 1:4 of petroleum ether is obtained as eluant, eluent To the sticky shape solid (0.28g, yield 53%) of yellow, it is directly used in and reacts in next step.
Embodiment 3
D (A-Ar) based on ten unitary condensed ring centronucleus of carbazole2Type target compound TBTDBC (DPP)2、 TBTDBC (DPP-Cz)2、TBTDBC(DPP-Th)2With TBTDBC (DPP-ST)2Synthetic route it is as shown below.
Wherein Ar are as follows:
Embodiment 4
Target compound TBTDBC (DPP)2Synthesis.
Sequentially added in 100mL dry there-necked flask compound Br-DPP (185mg, 0.22mmol), 10 mL toluene, Tetrakis triphenylphosphine palladium (Pd (PP3)4, 13mg, 0.01mmol) and TBTDBC- [Sn (CH3)3]2(150mg, 0.10mmol).Nitrogen Magnetic agitation under gas shielded is warming up to 110 DEG C, and back flow reaction is for 24 hours.Then reaction solution is cooled to room temperature, is quenched with 5mL water It goes out, and three times with chloroform extraction (20mL).Merge organic phase, anhydrous magnesium sulfate dries, filters, and rotation removes solvent, obtains black The crude product of color.Crude product uses silica gel as stationary phase, and the methylene chloride for being 1:3 with volume ratio: petroleum ether is that eluant, eluent carries out Column chromatography for separation obtains violet solid TBTDBC (DPP)2(150mg, yield 61%).1H NMR(400MHz,CDCl3)δ (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+].
Embodiment 5
Target compound TBTDBC (DPP-Cz)2Synthesis.
Compound Br-DPP-CZ (243mg, 0.22 mmol), 10mL first are sequentially added in 100mL dry there-necked flask Benzene, tetrakis triphenylphosphine palladium (Pd (PP3)4, (13mg, 0.01mmol) and TBTDBC- [Sn (CH3)3]2(150mg, 0.10mmol).Magnetic agitation under nitrogen protection is warming up to 110 DEG C, and back flow reaction is for 24 hours.Then reaction solution is cooled to room temperature, It is quenched with 5mL water, and three times with chloroform extraction (20mL).Merge organic phase, anhydrous magnesium sulfate is dried overnight, mistake Filter, rotation remove solvent, obtain the crude product of black.Crude product uses silica gel as stationary phase, the methylene chloride for being 1:3 with volume ratio: Petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains black solid TBTDBC (DPP-Cz)2(157mg, yield 52%).1H NMR(400MHz,CDCl3)δ(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+].
Embodiment 6
Target compound TBTDBC (DPP-Th)2Synthesis.
Compound Br-DPP-Th (225mg, 0.22mmol), 10mL first are sequentially added in 100mL dry there-necked flask Benzene, tetrakis triphenylphosphine palladium (Pd (PP3)4, 13mg, 0.01mmol) and TBTDBC- [Sn (CH3)3]2(150mg,0.10mmol)。 The magnetic agitation under the atmosphere of nitrogen protection is warming up to 110 DEG C, and back flow reaction is for 24 hours.Then reaction solution is cooled to room temperature, is used 5mL water is quenched, and three times with chloroform extraction (20mL).Merge organic phase, then is washed with 3 × 40mL saturated common salt It washs, the dry organic phase of anhydrous magnesium sulfate, filtering, rotation removes solvent, and it is 1:3's with volume ratio that crude product, which uses silica gel as stationary phase, Methylene chloride: petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains black solid TBTDBC (DPP-Th)2(156mg, Yield 55%).1H NMR(400MHz,CDCl3)δ(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+].
Embodiment 7
Target compound TBTDBC (DPP-ST)2Synthesis.
Compound Br-DPP-ST (232mg, 0.22mmol), 10mL first are sequentially added in 100mL dry there-necked flask Benzene, tetrakis triphenylphosphine palladium (Pd (PP3)4, 13mg, 0.01mmol) and TBTDBC- [Sn (CH3)3]2(150mg, 0.10mmol). Magnetic agitation under nitrogen protection is warming up to 110 DEG C, and back flow reaction is for 24 hours.Then reaction solution is cooled to room temperature, with 5mL water It is quenched, and three times with chloroform extraction (20mL).Merge organic phase, then with 3 × 40mL saturated common salt water washing, it is anhydrous Magnesium sulfate dries organic phase, filtering, and rotation removes solvent, and crude product uses silica gel as stationary phase, the dichloromethane for being 1:3 with volume ratio Alkane: petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains black solid TBTDBC (DPP-ST)2(169mg, yield 58%).1H NMR(400MHz,CDCl3)δ(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+].
Embodiment 8
D(A-Ar)2The production and performance test of the performance characterization and its photovoltaic device of type small molecule photovoltaic material.
D(A-Ar)2Type small molecule photovoltaic material1H NMR spectra passes through Bruker Dex-400NMR Instrument measuring, mass spectrum It is measured using the MALDI TOF mass spectrograph of Bruker Bifie, uv-visible absorption spectra passes through HP-8453 ultraviolet-visible Spectrometer measurement.
Based on D (A-Ar)nThe photovoltaic device of type small molecule material includes: indium tin oxide target (ITO) electro-conductive glass anode layer, oxygen Change zinc (ZnO) anode layer (30nm).Active layer is by the small molecule material and PC71BM, which is blended, constitutes (20nm), blending ratio column For 1:1.5, cathode is by MoO3(10nm)/Ag (100nm) layer is constituted.
Hole mobility device architecture be Glass/ITO/PEDOT:PSS (10nm)/active layer (20 nm)/ MoO3It is tested under (10nm)/Au (100nm).
Embodiment 9
Small molecule TBTDBC (DPP)2Photophysics and its Photovoltaic Device Performance
TBTDBC(DPP)2Ultra-violet absorption spectrum in solid film is as shown in Figure 2.Wherein the figure of absorption spectrum is substantially It is identical, but absorption peak has different degrees of red shift, this is because in solid film caused by π-pi accumulation.Peak position calculates by The optical band gap E of the materialg optFor 1.80eV.
TBTDBC(DPP)2Cyclic voltammetry curve in solid film is as shown in Figure 4.It shows two groups of reversible oxidations Peak can be attributed to the oxidation peak of donor monomer and receptor unit respectively.Thus the HOMO energy level and lumo energy of the material are obtained Respectively -5.23eV and -3.12eV.
TBTDBC(DPP)2With PC71The mixed proportion of BM is J-V curve graph such as Fig. 5 institute under 1:1.5 (w/w, 20mg/mL) Show.Under this condition, the short circuit current of device is 5.76mA/cm2, open-circuit voltage is 0.86 V, fill factor 70.1%, light Lying prostrate efficiency is 3.47%.
TBTDBC(DPP)2With PC71The mixed proportion of BM is EQE curve graph such as Fig. 6 under 1:1.5 (w/w, 20mg/mL) It is shown.The EQE test scope that the figure is shown is 300-750nm, there is maximum EQE value at 480nm, is 37%.
TBTDBC(DPP)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1.5 (w/w, 20mg/mL)1/2-V Curve is as shown in fig. 7, its hole mobility is up to 2.05 × 10-4cm2V-1s-1。
Embodiment 10
Small molecule TBTDBC (DPP-Cz)2Photophysics and its Photovoltaic Device Performance
TBTDBC(DPP-Cz)2Ultra-violet absorption spectrum in solid film is as shown in Figure 10.The wherein figure of absorption spectrum It is roughly the same, but absorption peak has different degrees of red shift, this is because in solid film caused by π-pi accumulation.Peak position is counted by Calculate the optical band gap E of the materialg optFor 1.68eV.
TBTDBC(DPP-Cz)2Cyclic voltammetry curve in solid film is as shown in figure 11.Its show two groups it is reversible Oxidation peak can be attributed to the oxidation peak of donor monomer and receptor unit respectively.Thus the HOMO energy level and LUMO of the material are obtained Energy level is respectively -5.31eV and -3.19eV.
TBTDBC(DPP-Cz)2With PC71The mixed proportion of BM be 1:1.5 (w/w, 20mg/mL) under J-V curve graph such as Shown in Figure 12.Under this condition, the short circuit current of device is 5.31mA/cm2, open-circuit voltage 0.89V, fill factor is 65.8%, photovoltaic efficiency 3.11%.
TBTDBC(DPP-Cz)2With PC71The mixed proportion of BM be 1:1.5 (w/w, 20mg/mL) under EQE curve graph such as Shown in Figure 13.The EQE test scope that the figure is shown is 300-750nm, there is maximum EQE value at 480nm, is 35%.
TBTDBC(DPP-Cz)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1.5 (w/w, 20mg/mL)1 /2- V curve is as shown in figure 14, and hole mobility is up to 1.74 × 10-4cm2V-1s-1。
Embodiment 11
Small molecule TBTDBC (DPP-Th)2Photophysics and its Photovoltaic Device Performance
TBTDBC(DPP-Th)2Ultra-violet absorption spectrum in solid film is as shown in figure 17.The wherein figure of absorption spectrum It is roughly the same, but absorption peak has different degrees of red shift, this is because in solid film caused by π-pi accumulation.Peak position is counted by Calculate the optical band gap E of the materialg optFor 1.79eV.
TBTDBC(DPP-Th)2Cyclic voltammetry curve in solid film is as shown in figure 18.Its show two groups it is reversible Oxidation peak can be attributed to the oxidation peak of donor monomer and receptor unit respectively.Thus the HOMO energy level and LUMO of the material are obtained Energy level is respectively -5.20eV and -3.39eV.
TBTDBC(DPP-Th)2With PC71The mixed proportion of BM be 1:1.5 (w/w, 20mg/mL) under J-V curve graph such as Shown in Figure 19.Under this condition, the short circuit current of device is 4.51mA/cm2, open-circuit voltage 0.77V, fill factor is 58.7%, photovoltaic efficiency 2.04%.
TBTDBC(DPP-Th)2With PC71The mixed proportion of BM is EQE curve graph such as figure under 1:1.5 (w/w, 20mg/mL) Shown in 20.The EQE test scope that the figure is shown is 300-750nm, there is maximum EQE value at 490nm, is 27%.
TBTDBC(DPP-Th)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1.5 (w/w, 20mg/mL)1 /2- V curve is as shown in figure 21, and hole mobility is up to 4.62 × 10-5cm2V-1s-1。
Embodiment 12
Small molecule TBTDBC (DPP-ST)2Photophysics and its Photovoltaic Device Performance
TBTDBC(DPP-ST)2Ultra-violet absorption spectrum in solid film is as shown in figure 24.The wherein figure of absorption spectrum It is roughly the same, but absorption peak has different degrees of red shift, this is because in solid film caused by π-pi accumulation.Peak position is counted by Calculate the optical band gap E of the materialg optFor 1.75eV.
TBTDBC(DPP-ST)2Cyclic voltammetry curve in solid film is as shown in figure 25.Its show two groups it is reversible Oxidation peak can be attributed to the oxidation peak of donor monomer and receptor unit respectively.Thus the HOMO energy level and LUMO of the material are obtained Energy level is respectively -5.24eV and -3.44eV.
TBTDBC(DPP-ST)2With PC71The mixed proportion of BM be 1:1.5 (w/w, 20mg/mL) under J-V curve graph such as Shown in Figure 26.Under this condition, the short circuit current of device is 5.25mA/cm2, open-circuit voltage 0.81V, fill factor is 63.7%, photovoltaic efficiency 2.71%.
TBTDBC(DPP-ST)2)2With PC71The mixed proportion of BM is the EQE curve graph under 1:1.5 (w/w, 20mg/mL) As shown in figure 27.The EQE test scope that the figure is shown is 300-750nm, there is maximum EQE value at 505nm, is 33%.
TBTDBC(DPP-ST)2With PC71The J of single-electron device when the mixed proportion of BM is 1:1.5 (w/w, 20mg/mL)1 /2- V curve is as shown in figure 28, and hole mobility is up to 3.31 × 10-5cm2V-1s-1。
Despite the incorporation of preferred embodiment, the present invention is described, but the present invention is not limited to the above embodiments, It should be understood that appended claims summarise the scope of the present invention.Under the guidance of present inventive concept, those skilled in the art It should be recognized that certain change that various embodiments of the present invention scheme is carried out, it all will be by claims of the present invention Spirit and scope covered.

Claims (8)

1. the D (A-Ar) based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric compound, it is characterised in that have shown in Formulas I Molecular structure.
Formulas I: D (A-Ar)2Type organic photoelectric compound
Wherein, A is the conjugate unit with electron withdrawing properties；
Ar is that the end of hydrogen atom, fluorine atom or functionalization is conjugated donor monomer；
D is based on ten unitary condensed ring conjugate planes centronucleus of carbazole；X is S, O or Se atom of the same clan；R is independently selected from C16~ C20Branched alkyl is a kind of.
2. the D (A-Ar) according to claim 1 based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric compound, it is special Sign is:
The A is the conjugate unit with electron withdrawing properties, and A one of has the following structure:
Wherein, R1For independently selected from C6~C12Branched alkyl or straight chained alkyl are a kind of in alkyl.
3. the D (A-Ar) according to claim 1 based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric compound, it is special Sign is:
End Ar is H, F or condensed-nuclei aromatics unit, wherein Ar one of has the following structure:
R1For independently selected from C6~C12Branched alkyl or straight chained alkyl are a kind of in alkyl.
4. the D (A-Ar) according to claim 1 based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric compound, it is special Sign is: the D (A-Ar)2Type organic photoelectric compound is with one of flowering structure
5. the D (A-Ar) according to claim 1-4 based on ten unitary condensed ring plane kernel of carbazole2Type organic photoelectric Compounds process for production thereof, it is characterised in that:
The first step, alkylated 2,7-, the bis- iodo- carbazole of bromo- 3,6- bis- are dissolved in toluene, and 2.0 are added in inert gas environment and rubs 2- tin trimethyl benzene [b] thiophene of your corresponding equivalent, 1%~5% four (triphenylphosphines) close palladium, and heating reflux reaction is overnight, After reaction, it extracts, dry, column Chromatographic purification obtains product M2；
Product M2 is dissolved in toluene by second step, and the tin reagent of 2~3 molar equivalents, 1%~5% four (triphenylphosphines) are added Conjunction palladium, heating reflux reaction 2~10 hours；After reaction, it is concentrated, extracts, dry, column Chromatographic purification obtains product M3；
Third step dissolves product M3 adding into dichloromethane, while the nitromethane of 1~2mL, inert gas shielding is added Under under confined conditions, select 275nm ultraviolet light under in room temperature reaction 5~8 hours, saturated ammonium chloride is added after reaction Solution, extraction, drying, column Chromatographic purification, recrystallization, obtains centronucleus product M4；
Product M4 is added in anhydrous tetrahydrofuran solution and dissolves by the 4th step, and it is Celsius to be cooled to -78 under inert gas shielding N-BuLi (0.97mL, 1.55mmol, 1.6M) solution is slowly added dropwise into wherein, 3h is reacted, by SnBu by degree3Cl adds rapidly Enter wherein, after the reaction was continued 1h, reaction system is transferred at room temperature, 16h is reacted；After being quenched with water, extraction, decompression rotation Except solvent obtains the crude product of yellow, viscous, crude product is through neutral alumina column chromatography for separation, anhydrous magnesium sulfate is dry, filtering, Decompression rotation removes solvent, and finally using methylene chloride: petroleum ether obtains the sticky shape solid M5 of yellow as eluant, eluent；
Monomer Br-A-Ar is dissolved in toluene under 5th step, nitrogen protection, addition tetrakis triphenylphosphine palladium, intermediate product M5, Reaction system back flow reaction is stayed overnight, it is then cooling, be quenched, extracted with water, anhydrous magnesium sulfate is dry, filtering, decompression rotation Except solvent, obtain lurid crude product, crude product is using methylene chloride: petroleum ether carries out column chromatography for separation as eluant, eluent, obtains yellow Solid powder M6；
Its reaction route is as follows:
6. the D (A-Ar) based on ten unitary condensed ring plane kernel of carbazole according to prepared by claim 52Type organic photoelectric compound Application, it is characterised in that: the polynary fused-ring derivatives of the carbazole of preparation have high hole mobility, can be used as active layer and answer For organic solar batteries, organic field effect tube, organic electroluminescent LED and organic near infrared photodetector In device.
7. D (A-Ar) according to claim 62The application of type organic photoelectric compound, it is characterised in that: the active layer Thickness is between 20 nanometers~1000 nanometers.
8. D (A-Ar) according to claim 62The application of type organic photoelectric compound, it is characterised in that: the active layer It is to be realized by solution processing method, including spin coating, brushing, spraying, dip-coating, roller coating, silk-screen printing, printing or inkjet printing side Method；Wherein solvent for use is organic solvent.
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CN112661771A (en) * 2020-12-18 2021-04-16 华南理工大学 Star-shaped fluorescent material based on asymmetric carbazole condensed rings and preparation method and application thereof
CN112707906A (en) * 2020-12-24 2021-04-27 安徽秀朗新材料科技有限公司 Novel organic electroluminescent material based on benzopyrrole diketone and application thereof
CN114957237A (en) * 2022-01-02 2022-08-30 东华理工大学 D (A-Ar) taking alkyl modified vat orange 3 as central nucleus 2 Synthesis and application of small organic molecules

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CN111153894A (en) * 2020-01-05 2020-05-15 浙江大学 Arylamine compound and application thereof in photoelectric device
CN111153894B (en) * 2020-01-05 2021-05-14 浙江大学 Arylamine compound and application thereof in photoelectric device
CN112661771A (en) * 2020-12-18 2021-04-16 华南理工大学 Star-shaped fluorescent material based on asymmetric carbazole condensed rings and preparation method and application thereof
CN112707906A (en) * 2020-12-24 2021-04-27 安徽秀朗新材料科技有限公司 Novel organic electroluminescent material based on benzopyrrole diketone and application thereof
CN112707906B (en) * 2020-12-24 2023-04-07 安徽秀朗新材料科技有限公司 Novel organic electroluminescent material based on benzopyrrole diketone and application thereof
CN114957237A (en) * 2022-01-02 2022-08-30 东华理工大学 D (A-Ar) taking alkyl modified vat orange 3 as central nucleus 2 Synthesis and application of small organic molecules
CN114957237B (en) * 2022-01-02 2024-02-02 东华理工大学 Alkyl-modified vat orange 3-centered core D (A-Ar) 2 Synthesis and application of small organic molecules

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