CN114751922B - D (A) based on diaryl and incorporating a fused ring unit 1 -π-A 2 ) 2 Conjugated small molecule and preparation method thereof - Google Patents

D (A) based on diaryl and incorporating a fused ring unit 1 -π-A 2 ) 2 Conjugated small molecule and preparation method thereof Download PDF

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CN114751922B
CN114751922B CN202210516311.8A CN202210516311A CN114751922B CN 114751922 B CN114751922 B CN 114751922B CN 202210516311 A CN202210516311 A CN 202210516311A CN 114751922 B CN114751922 B CN 114751922B
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彭文红
吴涛
邓继勇
陶强
张伟杰
颜东
匡纪炜
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Hunan Institute of Engineering
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Abstract

The invention relates to a diaryl-based D (A) with a fused ring unit 1 ‑π‑A 2 ) 2 Conjugated small molecules and a preparation method thereof. The conjugated micromolecule takes diaryl with rigid plane structure and introduces condensed rings as electron-pushing (D) units, takes thiophene as pi-bridge units, and selects and matches electron-withdrawing groups A with different properties 1 A is a 2 A series of narrow band gap small molecule photoactive layer materials capable of absorbing near infrared light are constructed. The material has good solubility, near infrared light absorption capacity and proper energy level; meanwhile, the solar cell has a more ordered intermolecular stacking state, and the spectrum of the ultra-narrow band gap can absorb more sunlight to obtain high short-circuit current. The material can become an electron donor or electron acceptor material in the photoactive layer by adjusting the electron withdrawing characteristic of the binary acceptor unit, is suitable for being used as the electron donor or electron acceptor material, and has better popularization and application prospects.

Description

D (A) based on diaryl and incorporating a fused ring unit 1 -π-A 2 ) 2 Conjugated small molecule and preparation method thereof
Technical Field
The invention relates to the technical field of organic photovoltaics, in particular to a D (A) based on diaryl and led to a condensed ring unit 1 -π-A 2 ) 2 Conjugated small molecules and a preparation method thereof.
Background
Organic photovoltaic cells have received wide attention from global researchers due to their low cost, light weight, solution-fabricable large-area flexible devices, and the like. For more than twenty years, fullerene derivatives (e.g. PC 61 BM、PC 71 BM, etc.) has the advantages of greater electron affinity, higher electron mobility, isotropic electron transport capacity, etcIs widely used as an electron acceptor material, realizes the Photoelectric Conversion Efficiency (PCE) of a device of 11 percent (such as Nat. Energy,2016, 1:15027), and plays a significant role in the rapid development of organic photovoltaic cells. However, the defects of the material, such as high preparation and purification cost, weak absorption capacity in a visible light region, difficult energy level control and the like, limit the further improvement of the performance of the organic photovoltaic cell to a certain extent. Moreover, most of the active layer donor materials used in the organic photovoltaic cell systems reported in the general literature only absorb visible light in the solar spectrum, and most of absorption peaks are distributed between 400 and 750nm, and about 48% of infrared light is not effectively utilized. If an ideal active layer material with near infrared absorption function, the absorption of which can be widened to 1000nm, can be explored, the PCE of the organic photovoltaic cell is expected to be further improved, and thus the commercialized application is realized. Therefore, it is important to develop a highly efficient narrow bandgap active layer material.
In recent years, the rise of non-fullerene electron acceptor materials opens up a new way for developing narrow bandgap organic active layer materials with near infrared absorption. At present, reported near-infrared non-fullerene small molecule acceptor materials all adopt an A-D-A or A-pi-D-pi-A type molecule construction strategy, remarkable progress is achieved, PCE of related devices breaks through 18%, and infinite potential is shown. However, the types of ultra-narrow band gap photovoltaic materials are still limited, and the design and development of novel near infrared active layer materials are critical for the preparation of organic photovoltaic cells with high energy conversion efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a brand new D (A) 1 -π-A 2 ) 2 Narrow band gap conjugated small molecular material and preparation method thereof, D (A) 1 -π-A 2 ) 2 The conjugated micromolecule has the determined molecular structure and molecular weight, is easy to synthesize and purify, has high batch repeatability, has narrower band gap and has excellent near infrared absorption performance.
To achieve the above object, the present invention provides a diaryl-based composition comprisingAnd introducing D (A) of condensed ring unit 1 -π-A 2 ) 2 The conjugated small molecule has a structural general formula shown in formula I:
Figure BDA0003639674350000021
wherein R is 1 One selected from the following groups: (1) Having C atoms 5 ～C 30 Straight-chain or branched alkyl, alkoxy or alkylthio groups; (2) Having C atoms 5 ～C 30 Aryl or heteroaryl of (a);
x is any one of O, S, se heteroatoms;
electron withdrawing group A 1 One selected from the following groups:
Figure BDA0003639674350000022
wherein: r is R 2 Is C 5 ～C 30 A linear or branched alkyl group;
electron withdrawing group A 2 One selected from the following groups:
Figure BDA0003639674350000023
wherein: x is X 1 、Y 1 Is any one of a hydrogen atom, a fluorine atom or a chlorine atom; r is R 3 Is C 5 ～C 30 Straight or branched alkyl groups.
Preferably, the D (A 1 -π-A 2 ) 2 The conjugated small molecule is shown in the following structural formulas II, III, IV or V:
Figure BDA0003639674350000031
Figure BDA0003639674350000041
wherein R is 1 Is C as the number of carbon atoms 5 ～C 30 Straight-chain or branched alkyl, alkoxy or alkylthio groups; r is R 2 Is C 5 ～C 30 A linear or branched alkyl group; r is R 3 Is C 5 ～C 30 A linear or branched alkyl group;
x is one of O, S, se heteroatoms.
Preferably, the D (A 1 -π-A 2 ) 2 The conjugated small molecule has a structural formula shown in the following formula VI or VII:
Figure BDA0003639674350000042
based on a general inventive concept, the present invention also provides a diaryl-based fused ring unit-incorporated D (A 1 -π-A 2 ) 2 The preparation method of the conjugated small molecule comprises the following steps:
s1, A substituted with monobromo 1 The unit compound and boric acid, boric acid ester or organic tin compound containing aldehyde group aromatic ring or aromatic heterocyclic ring are subjected to cross coupling reaction under the catalysis of palladium catalyst to obtain an intermediate compound;
s2, brominating the intermediate compound obtained in the step S1, and then carrying out cross coupling reaction with a central condensed ring double-tin compound under the catalysis of a palladium catalyst to obtain a dialdehyde compound;
s3, the dialdehyde compound obtained in the step S2 is subjected to electron withdrawing group A 2 Condensation reaction to obtain the product D (A) 1 -π-A 2 ) 2 Conjugated small molecules.
Preferably, the palladium catalyst is added in an amount of 3 to 10% by mol in the steps S1 and S2.
Preferably, the molar ratio of the intermediate compound after bromination in the step S2 to the central fused ring bistin compound is 2-5:1.
Compared with the prior art, the conjugated small molecular material developed by the invention has the following advantages:
1. the invention provides a diaryl-based D (A) with a fused ring unit 1 -π-A 2 ) 2 The molecular structure of the conjugated small molecule is characterized in that: the diaryl is used for introducing condensed rings as electron-pushing (D) units, thiophene is used as pi bridge units, and electron-withdrawing groups A with different properties are selected and matched 1 A is a 2 A class of narrow band gap conjugated small molecule active layer materials capable of absorbing near infrared light is constructed. Due to the rigid planar structure of the diaryl and indacene fused ring units, D (A 1 -π-A 2 ) 2 The configuration has the function of superimposed D-A, the multi-substituent on the condensed ring unit has good dissolution regulating capability, and the binary electron acceptor unit (A 1 ，A 2 ) The material has better energy level adjusting capability, so that the material has good solubility, near infrared light absorption capability and proper energy level;
2. the conjugated micromolecular material provided by the invention has more ordered intermolecular accumulation state, and the material with ultra-narrow bandwidth can absorb more sunlight to obtain high short-circuit current; the material can become an electron donor or electron acceptor material in the photoactive layer by adjusting the electron withdrawing characteristic of the binary acceptor unit, and is suitable for being used as the electron donor or electron acceptor material; the infrared light absorbing material has excellent near infrared absorption performance, can be used as a photoactive layer material to improve the sunlight utilization rate of the device, can also be used as an infrared detection material to obtain a small molecular photoelectric detection device with higher detection rate, and can be widely applied to organic photovoltaic cells and organic photoelectric detectors;
3. the invention provides a diaryl-based D (A) with a fused ring unit 1 -π-A 2 ) 2 The conjugated micromolecule has definite molecular structure and molecular weight, excellent stability, easy synthesis and purification, high batch repeatability and good application prospect.
Drawings
FIG. 1 shows a conjugated molecule IDT (DPP-TDRCN) in experimental example 1 of the present invention 2 Is a thermal weight loss curve of (2);
FIG. 2 shows the conjugated molecule IDT (TID-TDRCN) of experimental example 1 of the present invention 2 Is a thermal weight loss curve of (2)
FIG. 3 shows the conjugated molecule IDT (DPP-TDRCN) of experimental example 1 of the present invention 2 Is a differential scanning calorimetric curve of (2);
FIG. 4 shows a conjugated molecule IDT (TID-TDRCN) in experimental example 1 of the present invention 2 Is a differential scanning calorimetric curve of (2);
FIG. 5 shows the conjugated molecule IDT (DPP-TDRCN) of experimental example 1 of the present invention 2 Ultraviolet-visible absorption spectrum of (a);
FIG. 6 shows a conjugated molecule IDT (TID-TDRCN) in experimental example 1 of the present invention 2 Ultraviolet-visible absorption spectrum of (a);
FIG. 7 shows the conjugated molecule IDT (DPP-TDRCN) of Experimental example 1 of the present invention 2 Cyclic voltammograms of (2);
FIG. 8 shows a conjugated molecule IDT (TID-TDRCN) in experimental example 1 of the present invention 2 Is a cyclic voltammogram of (c).
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. .
Example 1
Conjugated small molecule IDT (DPP-TDRCN) 2 Is synthesized by (a)
The synthetic route and the synthetic steps of the conjugated small molecule are as follows:
Figure BDA0003639674350000061
1. synthesis of Compound 2
In a 250mL three-necked flask, compound 1 (1.00 g,1.06 mmol), 5-aldehyde-2-thiopheneboronic acid (0.51 g,2.12 mmol), tetrakis (triphenylphosphine) palladium (25 mg,0.02 mmol), sodium bicarbonate (0.53 g,6.36 mmol) solution (15 mL distilled water) and 120mL tetrahydrofuran were added sequentially. And (3) carrying out reflux reaction for 24 hours at 85 ℃ under the protection of nitrogen, stopping the reaction, and cooling to room temperature. The reaction solution was transferred to a separating funnel, 50mL of distilled water was added, the organic solvent was removed by extraction with dichloromethane, drying over anhydrous magnesium sulfate, filtration, and distillation under reduced pressure, and the obtained crude product was separated by column chromatography using Petroleum Ether (PE): dichloromethane (DCM) (2:1, v:v) as an eluent to give compound 2 (0.74 g, 72%) as a blue solid.
2. Synthesis of Compound 3
In a 100mL single-port flask, compound 2 (700 mg,0.72 mmol), N-bromosuccinimide (67 mg,0.94 mmol) and tetrahydrofuran (50 mL) were sequentially added, the reaction was carried out at room temperature in the absence of light for 12 hours, the reaction solution was poured into water, the organic solvent was removed by extraction with methylene chloride, drying over anhydrous magnesium sulfate and distillation under reduced pressure, and the crude product obtained was separated by column chromatography using PE: DCM (2:1, v:v) as eluent to give Compound 3 (470 mg, 63%) as a bluish violet solid. 1 H NMR(400MHz,CDCl 3 )δ:9.90(s,1H),8.87(d,J＝4.1Hz,1H),8.68(d,J＝4.2Hz,1H),7.72(d,J＝4.0Hz,1H),7.47(d,J＝4.1Hz,1H),7.38(d,J＝3.9Hz,1H),7.23(d,J＝4.2Hz,1H),4.01(d,J＝7.6Hz,2H),3.94(d,J＝7.8Hz,2H),1.92-1.88(m,2H),1.38-1.14(m,64H),0.88-0.83(m,12H).
3. Synthesis of Compound 5
In a 50mL two-port flask, compound 3 (250 mg,0.24 mmol), compound 4 (133 mg,0.11 mmol), tetrakis (triphenylphosphine) palladium (13 mg,0.01 mmol) and toluene (25 mL) were successively added, and the mixture was refluxed at 110℃for 12 hours under nitrogen. Cooled to room temperature, poured into 200mL of anhydrous methanol, precipitated, suction filtered, and the crude product was separated by column chromatography using PE: DCM (1:2, v: v) as eluent to give compound 5 (250 mg, 80%) as a dark green solid. 1 H NMR(400MHz,CDCl 3 )δ:9.89(s,1H),8.94(d,J＝4.0Hz,1H),8.84(d,J＝4.0Hz,1H),7.71(d,J＝3.5Hz,1H),7.47(d,J＝4.0Hz,1H),7.42(s,1H),7.37(d,J＝4.0Hz,1H),7.30(d,J＝4.3Hz,1H),7.23(d,J＝4.4Hz,1H),7.17(t,J＝9.2Hz,4H),7.13-7.06(m,4H),4.02(t,J＝5.7Hz,4H),2.62-2.50(m,4H),2.01-1.85(m,2H),1.63-1.56(m,4H),1.39-1.15(m,78H),0.90-0.79(m,18H).
4. Conjugated small molecule IDT (DPP-TD)RCN) 2 Is synthesized by (a)
In a 50mL two-necked flask, compound 5 (230 mg,0.08 mmol), compound 6 (90 mg,0.49 mmol), triethylamine (0.5 mL) and chloroform (40 mL) were sequentially added, and the mixture was refluxed at 60℃for 12 hours under nitrogen. Cooling to room temperature, pouring into 200mL anhydrous methanol, precipitating, suction filtering, and separating by column chromatography with stone PE: DCM: ethyl acetate (EtOAc) (100:100:1, v: v) as eluent to obtain dark green solid compound IDT (DPP-TDRCN) 2 (122mg,47％)。 1 H NMR(400MHz,CDCl 3 )δ:8.96(d,J＝4.1Hz,1H),8.82(d,J＝3.8Hz,1H),8.04(s,1H),7.49(d,J＝4.0Hz,1H),7.43(d,J＝4.7Hz,2H),7.39(d,J＝3.9Hz,1H),7.30(d,J＝4.2Hz,1H),7.23(d,J＝4.2Hz,1H),7.18(t,J＝9.3Hz,4H),7.09(t,J＝9.3Hz,4H),4.36-4.30(m,2H),4.10-3.95(m,4H),2.63-2.51(m,4H),2.00-1.86(m,2H),1.64-1.56(m,4H),1.42(t,J＝7.1Hz,3H),1.39-1.12(m,76H),0.92-0.73(m,18H).MS(MALDI-TOF):calcd.for C 198 H 260 N 10 O 6 S 10 [M]+3196.90；found 3196.46.
Example 2
Conjugated small molecule IDT (TID-TDRCN) 2 Is synthesized by (a)
The synthetic route and the synthetic steps of the conjugated small molecule are as follows:
Figure BDA0003639674350000081
1. synthesis of Compound 8
In a 250mL three-necked flask, compound 7 (10 g,61.40 mmol), 2-ethylhexyl amine (11.9 g,92.10 mmol), copper powder (0.20 g,3.08 mmol), iodoketone (0.59 g,3.08 mmol), potassium phosphate (26.06 g,122.80 mmol), N, N-dimethylethanolamine (120 mL) were added sequentially, and the mixture was stirred under nitrogen at 80℃for 48 hours. After the reaction was stopped, cooled and suction-filtered, the solvent was removed from the resulting filtrate by rotary distillation under reduced pressure, and the residue was distilled under reduced pressure to give Compound 8 (5.2 g, 40%) as a tan liquid. 1 H NMR(400MHz,CDCl 3 )δ:7.18(dd,1H),6.65(dd,1H),5.95(s,1H),3.61(s,1H),3.01(d,2H),1.63(m,1H),1.30-1.35(m,8H),0.92(m,6H).
2. Synthesis of Compound 9
In a 500mL two-necked flask, oxalyl chloride (4.06 g,31.98 mmol) was added and placed in an ice bath at 0deg.C. Compound 8 (5.2 g,24.60 mmol) was dissolved in 10mL of methylene chloride and then slowly dropped into the reaction system. After completion of the dropwise addition, the reaction was continued for 0.5h, followed by dropwise addition of a solution of triethylamine (8.6 mL,61.75 mmol) diluted with 10mL of methylene chloride. The reaction was transferred to room temperature and allowed to react for 3 hours, and the reaction was stopped. The reaction was poured into 100mL of ice water, extracted with dichloromethane, and the organic phases combined. The organic phase was washed 3 times with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the organic solvent, and the remaining solution was eluted with PE: etOAc (3:1, v:v) and separated by column chromatography to give compound 9 (3.00 g, 46%) as a reddish brown liquid. 1 H NMR(400MHz,CDCl 3 )δ:8.00(d,1H),6.78(d,1H),3.61(d,2H),1.79(m,1H),1.26-1.33(m,8H),0.89(m,6H).
3. Synthesis of Compound 10
In a 100mL three-necked flask, compound 9 (3.00 g,11.30 mmol), L.sub.Hemsl (2.29 g,5.65 mmol) and 40mL toluene were sequentially added, reacted at 80℃for 2 hours under nitrogen protection, cooled to room temperature, the reaction solution was poured into water, extracted with methylene chloride, the combined organic phases were dried over anhydrous magnesium sulfate, and the organic solvent was distilled off under reduced pressure, and the obtained crude product was separated by column chromatography using PE: DCM (3:1, v:v) as an eluent to obtain purple solid compound 10 (1.44 g, 51%). 1 H NMR(400MHz,CDCl 3 )δ:7.53(d,J＝5.2Hz,1H),6.79(d,J＝5.2Hz,1H),3.71-3.68(m,2H),1.92-1.76(m,1H),1.45-1.20(m,8H),0.96-0.81(m,6H).
4. Synthesis of Compound 11
In a 100mL single-necked flask, compound 10 (1.44 g,2.89 mmol) was dissolved in 60mL tetrahydrofuran, cooled to 0℃in the dark, and a solution of N-bromosuccinimide (0.57 g,3.18 mmol) in tetrahydrofuran (5 mL) was added dropwise. The reaction was continued until the starting material was almost completely disappeared, the reaction solution was poured into water, extracted with dichloromethane, the combined organic phases were dried over anhydrous magnesium sulfate, the organic solvent was removed by distillation under the reduced pressure, and the obtained crude product was separated by column chromatography using PE: DCM (5:1, v: v) as an eluent to give compound 11 (0.73 g, 44%) as a bluish violet solid. 1 H NMR(300MHz,CDCl 3 )δ:7.55(d,J＝5.2Hz,1H),6.84(s,1H),6.79(d,J＝5.2Hz,1H),3.70-3.64(m,4H),1.85-1.79(m,2H),1.44-1.20(m,16H),0.96-0.83(m,12H).
5. Synthesis of Compound 12
In a 50mL two-port flask, compound 11 (730 mg,1.26 mmol), (5- (1, 3-dioxo-2-yl) thiophen-2-yl) tributyltin (729 mg,1.64 mmol), tetrakis (triphenylphosphine) palladium (44 mg,0.04 mmol) and toluene (20 mL) were successively added and reacted under reflux at 110℃for 24h under nitrogen. The reaction was stopped, and the toluene solvent was distilled off under reduced pressure. The residue was dissolved in 20mL of tetrahydrofuran, and an aqueous hydrochloric acid solution (10 mL ) was added thereto, followed by stirring at room temperature overnight. The reaction was transferred to a separatory funnel, extracted with dichloromethane, the combined organic phases were dried over anhydrous magnesium sulfate, the organic solvent was removed by distillation under reduced pressure, and the crude product obtained was separated by column chromatography using PE: DCM (1:1, v: v) as eluent to give dark indigo solid compound 12 (45 mg, 59%). 1 HNMR(300MHz,CDCl 3 )δ:9.89(s,1H),7.70(d,J＝4.0Hz,1H),7.58(d,J＝5.2Hz,1H),7.44(d,J＝4.0Hz,1H),7.00(s,1H),6.80(d,J＝5.2Hz,1H),3.76-3.65(m,4H),1.89-1.83(m,2H),1.47-1.22(m,16H),0.99-0.82(m,12H).
6. Synthesis of Compound 13
In a 100mL single-necked flask, compound 12 (45 mg,0.75 mmol), N-bromosuccinimide (160 mg,0.90 mmol) and tetrahydrofuran (45 mL) were sequentially added, the reaction was carried out at room temperature in the absence of light until the starting material was completely disappeared, the reaction solution was poured into water, extracted with dichloromethane, and the combined organic phases were dried over anhydrous magnesium sulfate. The organic solvent was removed by distillation under the reduced pressure, and the crude product obtained was separated by column chromatography using PE: DCM (2:1, v:v) as eluent to give Compound 13 (366 mg, 71%) as a green solid. 1 H NMR(300MHz,CDCl 3 )δ:9.88(s,1H),7.69(d,J＝4.1Hz,1H),7.42(d,J＝4.0Hz,1H),6.96(s,1H),6.82(s,1H),3.71-3.64(m,4H),1.90-1.75(m,2H),1.44-1.21(m,16H),0.96-0.87(m,12H).
2.1 Synthesis of Compound 15
In a 50mL two-port flask, compound 13 (150 mg,0.22 mmol), compound 14 (128 mg,0.11 mmol), tetrakis (triphenylphosphine) palladium (44 mg,0.04 mmol) and toluene (20 mL) were successively added, and the mixture was refluxed at 110℃for 12 hours under nitrogen.Cooled to room temperature, poured into 200mL of anhydrous methanol, and a dark green precipitate is precipitated, filtered by suction, and the crude product is separated by column chromatography with PE: DCM (1:2, v: v) as eluent to obtain a dark green solid compound 15 (192 mg, 88%). 1 H NMR(400MHz,CDCl 3 )δ:9.85(s,1H),7.67(d,J＝3.9Hz,1H),7.43(s,1H),7.40(d,J＝3.9Hz,1H),7.35(s,1H),7.17(t,J＝6.5Hz,4H),7.10(t,J＝6.5Hz,4H),6.98(s,1H),6.81(s,1H),3.75-3.65(m,4H),2.63-2.52(m,4H),1.86(m,2H),1.65-1.57(m,4H),1.44-1.23(m,28H),0.98-0.82(m,18H).
7. Conjugated molecule IDT (TID-TDRCN) 2 Is synthesized by (a)
In a 50mL two-port flask, compound 15 (180 mg,0.09 mmol), compound 16 (80 mg,0.29 mmol), triethylamine (0.5 mL) and chloroform (30 mL) were successively added, and the mixture was refluxed at 60℃for 12 hours under nitrogen. Cooling to room temperature, pouring into 200mL anhydrous methanol, precipitating yellow-green precipitate, filtering, and separating the crude product by column chromatography with PE: DCM: etOAc (100:100:1, v: v) as eluent to obtain black yellow-green solid compound IDT (TID-TDRCN) 2 (120mg,54％)。 1 H NMR(400MHz,CDCl 3 )δ:7.99(s,1H),7.46-7.41(m,2H),7.39(d,J＝3.6Hz,1H),7.36(d,J＝3.8Hz,1H),7.18(t,J＝6.6Hz,4H),7.14-7.05(m,4H),6.96(s,1H),6.81(s,1H),4.23-4.12(m,2H),3.81-3.63(m,4H),3.81-3.63(m,4H),2.64-2.51(m,2H),1.89(d,J＝27.2Hz,2H),1.65-1.57(m,4H),1.50-1.19(m,38H),0.95-0.86(m,21H).MS(MALDI-TOF):calcd.for C 158 H 184 N 10 O 6 S 10 [M] + 2639.86；found 2639.84.
Experimental example 3
Conjugated small molecule IDT (DPP-TDRCN) prepared in example 1 2 And IDT (TID-TDRCN) obtained in example 2 2 Performance characterization of (2):
of the compounds synthesized 1 The H NMR spectrum was determined by Bruker Dex-300 NMR or 400NMR instrument; mass Spectrum (MS) is obtained by analysis and test of MALDI-TOF mass spectrometer with model Bruker Bifiex; a thermal weight loss (TGA) curve was tested using a thermal analyzer (model Perking-El TGA) at a ramp rate of 20 ℃/min; differential Scanning Calorimetric (DSC) curve was run through a TA DSCQ10 analyzer at 20℃under nitrogen atmosphereThe heating rate of min is tested; the ultraviolet-visible absorption spectrum was measured by a Shimadzu UV-800 ultraviolet-visible spectrophotometer; cyclic voltammograms were tested using a CHI630E electrochemical analyzer.
1. Conjugated small molecule IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 Is measured by the thermal stability of (2)
FIGS. 1 and 2 show conjugated small molecules IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 The 5% thermal weight loss temperature is 389 ℃ and 418 ℃ respectively, which shows that the thermal stability of the polymer reaches the application requirement of the organic solar cell.
2. Conjugated small molecule IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 Crystallization Performance measurement of (C)
Conjugated small molecule IDT (DPP-TDRCN) prepared in examples 1 and 2 2 And IDT (TID-TDRCN) 2 The DSC curves of (2) are shown in fig. 3 and 4, respectively. As can be seen from the results of FIGS. 3 to 4, a small molecule IDT (TID-TDRCN) 2 No melting and crystallization process during heating and cooling, indicating that it may be in an amorphous state; small molecule IDT (DPP-TDRCN) 2 A distinct endothermic peak occurs upon heating to 219 c, as there is a melting process at heating, and an exothermic peak occurs at 139 c during cooling, which is attributed to the crystallization process of the small molecules. Thus, small molecule IDT (DPP-TDRCN) 2 Has a more ordered intermolecular packing state.
3. Conjugated small molecule IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 Photophysical property measurement of (2)
FIGS. 5 and 6 show conjugated small molecules IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 As can be seen from the results of the graph, the ultraviolet-visible absorption spectra in chloroform solution and film state have broad and strong absorption in both the solution and film, wherein IDT (DPP-TDRCN) 2 Exhibits two distinct characteristic absorption peaks in the 300-900nm range, IDT (TID-TDRCN) 2 Two distinct characteristic absorption peaks are present in the 300-1100nm range; short-band absorption is attributed to pi-pi transition of molecular main chain, and long-band absorption peak is attributed to charge transfer from donor unit to acceptor unit in molecule(ICT) effect. The absorption of the film relative to the solution is significantly red shifted and vibration shoulders occur, which is a consequence of the enhanced molecular packing in the solid state. Through calculation, IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 The optical band gap of (a) is 1.40eV and 1.21eV (formula E g 1240/λ, where E g Is an optical bandgap, λ is the film maximum absorption sideband value). The result shows that the two small molecules are ultra-narrow band gap materials, so that more sunlight can be absorbed, and high short-circuit current can be obtained.
4. Conjugated small molecule IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 Electrochemical performance measurement of (2)
Conjugated small molecule IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 Bu at 0.1mol/L 4 NBF 4 /CH 2 Cl 2 The cyclic voltammogram in the solution is shown in FIGS. 7 and 8, according to equation E HOMO ＝-(E ox +4.80) eV, giving their HOMO levels of-5.16 eV and-5.07 eV, respectively. According to the calculation formula E LUMO ＝-(E red +4.80) eV, giving their LUMO levels of-3.56 eV and-3.64 eV, respectively. Thus, IDT (DPP-TDRCN) 2 And IDT (TID-TDRCN) 2 The electrochemical band gaps of (2) are 1.60eV and 1.43eV, respectively.
While the invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the specific embodiments described above, but it is intended that the appended claims be construed to cover the scope of the invention. It will be appreciated by those skilled in the art that certain changes to the embodiments of the invention are to be made in light of the inventive concepts and are to be covered by the spirit and scope of the appended claims.

Claims (1)

1. D (A) based on diaryl and incorporating a fused ring unit 1 -π-A 2 ) 2 The conjugated small molecule is characterized in that: said D (A) 1 -π-A 2 ) 2 The conjugated small molecule has a structural formula shown in the following formula VI or VII:
Figure FDA0004116367020000011
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