CN114920742A - Tri-or quintuple hetero [ n ] spiroalkene electron donor material and preparation method and application thereof - Google Patents

Tri-or quintuple hetero [ n ] spiroalkene electron donor material and preparation method and application thereof Download PDF

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CN114920742A
CN114920742A CN202210647969.2A CN202210647969A CN114920742A CN 114920742 A CN114920742 A CN 114920742A CN 202210647969 A CN202210647969 A CN 202210647969A CN 114920742 A CN114920742 A CN 114920742A
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donor material
electron donor
aromatic ring
spiroalkene
inner core
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谢素原
巫殷福
张玲
陈斌文
张前炎
邓林龙
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Xiamen University
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Abstract

The invention discloses a three-or five-fold hetero [ n ] helicene electron donor material and a preparation method and application thereof, wherein the electron donor material takes aza-caryophyllene as an inner core, the edge of the inner core is symmetrically connected with 4 or 5 aromatic ring pyrene structure units, adjacent aromatic ring pyrene structure units and the edge of the inner core form single [ n ] helicene, and the single [ n ] helicene comprises three or five-fold [ n ] helicene in total. The preparation method is simple and effective, the process is easy to control, and the synthesized hetero [ n ] helicene molecules with a triple or quintuple structure have higher stability and can be used as electron donor materials of organic solar cells, so that the stability and the efficiency of the organic solar cells are improved.

Description

Tri-or quintuple hetero [ n ] spiroalkene electron donor material and preparation method and application thereof
Technical Field
The invention relates to the technical field of solar cell materials, in particular to a tri-or quintuple hetero [ n ] spiroalkene electron donor material and a preparation method and application thereof.
Background
Solar cells are popular among researchers because they can directly convert solar energy into electric energy. Among the numerous solar cells, Organic Solar Cells (OSCs) have been widely studied for their solution processability, low cost, flexibility, and ease of fabrication in large areas. The photoelectric conversion efficiency of organic solar cells has continued to increase over the last two thirty years. Currently, the literature reports that the efficiency of organic solar cells reaches 19% (adv. mater, 2021,33,2102420), approaching the threshold of commercialization. With the advent of more and more new materials, organic solar cells are exhibiting unprecedented viability as a new type of cell.
In order to improve the stability and the photoelectric conversion efficiency of the organic solar cell, scientists optimize and improve the active layer of the organic solar cell. The electron donor material is one of the key components of the active layer of the organic solar cell, and the optimization of the donor material has very important significance for improving the efficiency and stability of the organic solar cell. At present, electron donor materials adopted by the organic solar cell are mainly polymers or organic small molecules based on a plane conjugated pi system. Although these donor materials have excellent photovoltaic performance, under heating or illumination conditions, aggregation between planar conjugated molecules of the cell based on the planar conjugated pi system donor material is easy to occur, so that the appearance of the active layer is unstable, the stability of the organic solar cell device is limited, and the commercial application of the organic solar cell is not facilitated. Therefore, the development of new electron donor materials to improve the stability of organic solar cells has become one of the keys to the further development of organic solar cells.
Disclosure of Invention
In order to solve the problems, the invention provides a tri-or penta-hetero [ n ] helicene electron donor material and a preparation method thereof, which are used for the electron donor material of an organic solar cell and improve the stability and efficiency of the organic solar cell.
The invention adopts the following technical scheme:
a three or five-fold hetero [ n ] helicene electron donor material takes azacarylene as an inner core, 4 or 5 aromatic ring pyrene structural units are symmetrically connected to the edge of the inner core, adjacent aromatic ring pyrene structural units and the edge of the inner core form single [ n ] helicene, the single [ n ] helicene comprises three or five-fold [ n ] helicene in total, and the chemical structural formula is as follows:
Figure BDA0003684734950000021
wherein n is the number of ortho-position fused aromatic rings, m is the number of aromatic ring pyrene structural units, and Q is an aromatic ring or aromatic ring pyrene structural unit selected from aromatic rings and derivatives thereof; r1 and R2 are independently selected from any one of H atom, aryl group, amino group, halogen atom or C1-10 linear or branched alkyl group, C1-10 linear or branched alkoxy group, C1-10 linear or branched alkylthio group and C1-10 linear or branched amine.
Further, the chemical structural formula of Q is any one of the following:
Figure BDA0003684734950000031
wherein, X is any one of oxygen atom, sulfur atom, selenium atom or nitrogen atom; R1-R8 are independently selected from any one of H atom, aryl group, amino group, halogen atom or C1-10 linear or branched alkyl group, C1-10 linear or branched alkoxy group, C1-10 linear or branched alkylthio group and C1-10 linear or branched amine.
Further, when the edge of the inner core is symmetrically connected with 5 benzopyrene structural units, Q is phenyl, R1 is propoxy, R2 is H atom, and m is equal to 5, the electron donor material is an aza-penta [7] spiro-alkenyl organic solar cell donor material, namely N-Q7H, and the chemical structural formula of the N-Q7H is as follows:
Figure BDA0003684734950000041
further, when 5 structural units of aromatic ring pyrene are symmetrically connected to the edge of the inner core, Q is naphthyl, R1 is dimethyl-phenyl, R2 is tert-butyl, and m is equal to 5, the electron donor material is an aza-pentadeca [9] spiroalkene-based organic solar cell donor material, namely N-Q9H, and the chemical structural formula of N-Q9H is as follows:
Figure BDA0003684734950000042
further, when 5 structural units of aromatic ring pyrene are symmetrically connected to the edge of the inner core, Q is benzothiophene, R1 is H atom, R2 is tert-butyl, and m is equal to 5, the electron donor material is a sulfur and aza-penta [9] spiroalkene-based organic solar cell donor material, namely SNQ9H, and the chemical structural formula of the SNQ9H is as follows:
Figure BDA0003684734950000051
further, when the edge of the inner core is symmetrically connected with 5 aromatic ring pyrene structural units, Q is thiophene, R1 is methyl, R2 is tert-butyl, and m is equal to 5, the electron donor material is a sulfur and aza-penta [7] spiro-alkenyl organic solar cell donor material, namely SNQ7H, and the chemical structural formula of the SNQ7H is as follows:
Figure BDA0003684734950000052
further, when 4 structural units of aromatic ring pyrene are symmetrically connected at the edge of the inner core, Q is thiophene, R1 is methyl, R2 is tert-butyl, and m is equal to 4, the electron donor material is a sulfur and aza-triplet [7] spiroalkene-based organic solar cell donor material, namely SNT7H, and the chemical structural formula of the SNT7H is as follows:
Figure BDA0003684734950000061
a preparation method of a tri-or penta-hetero [ n ] spiroalkene electron donor material comprises the following steps:
s1, carrying out carbon-hydrogen bond boronization on pentabenzoazacarylene and bisphenopinacol borate under the action of an iridium catalyst to obtain a pentabenzoazacarylene-pentaborate and a pentabenzoazacarylene-tetraboroborate reaction synthon;
s2, dissolving the tetra-or pentaboron ester compound of pentabenzo-aza-cyclotene and iodo terphenyl or derivative in an organic solvent at 130 ℃, heating and reacting for 12h under the action of alkali and palladium catalyst, performing Suzuki-Miyaura coupling reaction, and then performing intramolecular dehydrocyclization reaction through Scholl reaction to obtain the tri-or pentahetero [ n ] spirolene molecule used as the donor material of the organic solar cell.
Further, the base adopted in the Suzuki-Miyaura coupling reaction is any one or more of potassium carbonate, potassium phosphate and cesium carbonate; the organic solvent adopted in the Suzuki-Miyaura coupling reaction is N, N-dimethylformamide.
An application of a tri-or quintuplex [ n ] hetero [ n ] spiroalkene electron donor material in an organic solar cell.
After adopting the technical scheme, compared with the background technology, the invention has the following advantages:
1. the electron donor material is a unique triple or quintuple hetero [ n ] helicene structure taking aza-cyclocaryon as a core, has better solubility and electron donating property, has better energy level matching with a fullerene electron acceptor, is favorable for regulating and controlling the energy level of molecules, has non-planar molecules with a larger pi conjugated system, can regulate the accumulation of the molecules, forms a larger pi conjugated system for the whole donor molecule, obtains the electron donor material with higher stability, and can be used as the electron donor material of an organic solar cell, thereby improving the stability and the efficiency of the organic solar cell.
2. The electron donor material of the invention takes penta-aza-caryophyllene molecules as cores, introduces different aromatic rings or aromatic ring combination units to construct spiroalkene structures with different numbers of weight and different spiro numbers, and has the advantages that: firstly, non-planar azacarylene is used as a molecular inner core, so that the interaction force between donor molecules and acceptor materials such as fullerene can be effectively improved; secondly, the unique helical structure of the spiroalkene has better solubility in organic solvent; and thirdly, the azacarylene kernel has non-planar molecules with a larger pi conjugated system, so that a larger pi conjugated system is formed for the whole donor material molecule, and a foundation is provided for obtaining a spiroalkenyl electron donor material with wide spectral absorption.
3. The preparation method of the electron donor material is simple and effective, the process is easy to control, and the hetero [ n ] helicene molecular solar cell donor material with a triple or quintuple structure is synthesized for the first time.
4. The preparation process of the electron donor material is simple and convenient, a terphenyl or derivative unit is synthesized firstly, a reaction precursor is obtained by carrying out Suzuki-Miyaura coupling reaction with a pentabenzo-aza-cyclocarylene (aza-penta-zene-cocraninene) tetra-and pentaborate intermediate, and finally, intramolecular dehydrocyclization is carried out by Scholl reaction to synthesize a tri-or penta-hetero [ n ] spirolene molecule to be used as the donor material of the organic solar cell.
Drawings
FIG. 1 is a chemical structural diagram of an electron donor material of the present invention;
FIG. 2 is a mass spectrum of an electron donor material prepared according to example one of the present invention;
FIG. 3 shows an example of the preparation of an electron donor material according to the invention 1 HNMR spectrogram;
FIG. 4 is a mass spectrum of an electron donor material prepared in accordance with example two of the present invention;
FIG. 5 is a mass spectrum of an electron donor material prepared in example three of the present invention;
FIG. 6 is a photograph of a sample of the invention prepared in example IIIOf electron-donor materials 1 HNMR spectrogram;
FIG. 7 is a mass spectrum of an electron donor material prepared in accordance with example four of the present invention;
FIG. 8 is a mass spectrum of a donor material prepared in accordance with EXAMPLE five of the present invention;
fig. 9 is a J-V plot of an organic solar cell device prepared according to example six of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. The test methods described in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
Example one
The structural formula of the quintuple aza [7] helicene (N-Q7H) donor material of this example is:
Figure BDA0003684734950000081
the synthetic route is as follows:
Figure BDA0003684734950000082
(1) synthesis of Compound 3: a25 mL Schlenk tube was selected, placed in an appropriate magneton, and 106mg of Compound 1, 706mg of Compound 2, 115mg of tetrakis (triphenylphosphine) palladium and 396mg of potassium carbonate were added to the flask, and the gas was evacuated using a double calandria tube. Subsequently, 5mL of degassed N, N-dimethylformamide was injected into the reaction system, and reacted at 130 ℃ for 12 hours. The reaction was cooled to room temperature, extracted with dichloromethane and washed 3 times with water. Collecting the organic phase, Na 2 SO 4 And (5) drying and spin-drying. Separating and purifying by a silica gel chromatographic column, loading the sample by a dry method, and eluting by petroleum ether: dichloromethane ═ 1.5: 1. finally obtaining 112mg of compoundSubstance 3, yield: 52 percent. 1 H NMR(600MHz,CDCl 3 )δ＝7.20-7.17(t,J＝12Hz,2H),7.12-7.15(t,J＝12Hz,8H),6.82-6.83(d,J＝6Hz,6H),6.79-6.80(d,J＝6Hz,6H),6.73-6.70(m,6H),6.64-6.66(m,16H),6.50-6.47(t,J 1 ＝6Hz,J 2 ＝6Hz,8H),6.28-6.26(m,6H),6.24-6.22(d,J＝12Hz,4H),6.15-6.07(m,8H),3.71-3.69(t,J＝6Hz,4H),3.59-3.57(t,J＝6Hz,8H),3.55-3.53(t,J＝6Hz,8H),1.54-1.49(dt,J 1 ＝2Hz,J 2 ＝12Hz,4H),1.44-1.37(m,16H).0.75-0.72(t,J＝12Hz,6H),0.67-0.65(t,J＝6Hz,12H),0.62-0.60(t,J＝6Hz,12H) 13 C NMR(150MHz,CDCl 3 )δ＝158.97,158.93,158.90,158.87,158.74,158.61,158.48,158.42,143.59,143.40,130.06,130.04,130.02,130.00,129.97,129.95,129.24,129.23,129.15,129.12,128.16,128.11,127.56,127.36,122.92,122.87,122.45,122.43,117.04,116.97,116.45,69.67,69.59,69.55,22.38,22.29,22.27,10.47,10.41,10.36.HRMS(LC-MALDI-TOF/TOF)；m/z for C 154 H 135 NO 10 [M]calcd.2158.009,found:2158.004。
(2) Synthesis of Compound N-Q7H: selecting a 100mL Schlenk flask, placing an appropriate magneton, adding 43mg of Compound 3 and 91mg of dichlorodicyanoquinone (DDQ) to the flask, performing suction gas using a double-row tube, then adding 30mL of an anhydrous oxygen-free dichloromethane solution, placing the reaction system at 0 ℃ and stirring for 5 minutes, then adding 1.5mL of methanesulfonic acid, continuing the reaction at 0 ℃ for 4.5 hours, then adding hydrazine hydrate to quench, adding dichloromethane to dilute the reaction solution, washing with water until the aqueous layer is colorless, collecting the organic layer, Na 2 SO 4 And (5) drying and spin-drying. The compound N-Q7H was unstable on silica gel column and the final target product was isolated using high performance liquid chromatography.
The obtained N-Q7H had a clear mass spectrum as shown in FIG. 2 and a nuclear magnetic hydrogen spectrum as shown in FIG. 3, and the X-ray single crystal diffraction characterization as shown in Table 1 below. HRMS (LC-MALDI-TOF/TOF); m/z for C 154 H 115 NO 10 [M]calcd.2137.852,found:2137.855。
Table 1 table of X-ray crystallographic data of donor material prepared in example one;
Figure BDA0003684734950000101
example two
The structural formula of the quintuple aza [9] helicene (N-Q9H) donor material of this example is:
Figure BDA0003684734950000111
the synthetic route is as follows:
Figure BDA0003684734950000112
(1) synthesis of Compound 3: a25 mL Schlenk tube was taken, an appropriate magneton was placed, and 106mg of Compound 1, 664mg of Compound 2, 115mg of tetrakis (triphenylphosphine) palladium and 396mg of potassium carbonate were added to the bottle, and the gas was evacuated using a double calandria tube. Subsequently, 5mL of degassed N, N-dimethylformamide was injected into the reaction system, and reacted at 130 ℃ for 12 hours. The reaction was cooled to room temperature, extracted with dichloromethane and washed 3 times with water. Collecting the organic phase, Na 2 SO 4 And (5) drying and spin-drying. Separating and purifying by a silica gel chromatographic column, loading by a dry method, and eluting by petroleum ether: dichloromethane ═ 3: 1. finally 83mg of compound 3 are obtained, yield: 27 percent. HRMS (LC-MALDI-TOF/TOF); m/z for C 244 H 175 N[M]calcd.3118.372,found:3118.369。
(2) Synthesis of Compound N-Q9H: selecting a 100mL Schlenk flask, placing a suitable magneton, adding 43mg of Compound 3 and 91mg of dichlorodicyanobenzoquinone (DDQ) to the flask, purging with a double-row tube, then adding 30mL of anhydrous oxygen-free dichloromethane solution, allowing the reaction system to stand at room temperature and stirring for 5 minutes, then adding 0.3mL of trifluoromethanesulfonic acid, continuing to react at 30 ℃ for 30 minutes, then adding hydrazine hydrate to quench, adding dichloromethane to dilute the reaction solution, washing with water until the aqueous layer is colorless, collecting the organic layer, Na 2 SO 4 And (5) drying and spin-drying. The compound N-Q9H is unstable on silica gel column, and the final target product is high in useAnd (4) performing liquid chromatography separation. The obtained N-Q9H had a definite mass spectrum as shown in FIG. 4. HRMS (LC-MALDI-TOF/TOF); m/z for C 244 H 155 N[M]calcd.3098.216,found:3098.210。
EXAMPLE III
The structural formula of the pentadiazo, thia [9] helicene (SNQ9H) donor material of this example is:
Figure BDA0003684734950000121
the synthetic route is as follows:
Figure BDA0003684734950000122
(1) synthesis of Compound 3: selecting a 25mL Schlenk tube, putting a proper magneton, adding 106mg of compound 1, 619mg of compound 2, 115mg of tetrakis (triphenylphosphine) palladium and 396mg of potassium carbonate into the bottle, and using a double-row tube to perform air suction; subsequently, 5mL of degassed N, N-dimethylformamide was injected into the reaction system, and reacted at 130 ℃ for 24 hours. The reaction was cooled to room temperature, extracted with dichloromethane and washed 3 times with water. Collecting the organic phase, Na 2 SO 4 And (5) drying and spin-drying. Purifying and separating with silica gel chromatographic column, loading sample by dry method, and eluting with petroleum ether: dichloromethane ═ 3: 1. finally 155mg of compound 3 were obtained, yield: and 64 percent. 1 H NMR(400MHz,CD 2 Cl 2 )δ＝7.98-6.58(m,70H),1.49(m,45H). 13 C NMR(100MHz,CD 2 Cl 2 )δ＝150.69,150.55,150.30,143.98,143.85,140.36,139.54,139.42,139.37,138.31,138.01,137.62,136.83,135.91,135.20,135.13,135.02,134.73,133.95,133.49,131.52,130.33,129.22,128.58,128.44,128.28,128.22,128.17,128.12,127.33,127.18,126.87,125.93,125.71,125.62,124.86,123.96,123.88,123.81,123.71,123.66,123.63,123.55,123.37,123.30,123.21,123.11,121.74,121.67,34.73,34.68,34.66,31.06.HRMS(LC-MALDI-TOF/TOF)；m/z for C 164 H 115 NS 10 [M]calcd.2417.624,found:2417.783。
(2) Synthesis of compound SNQ9H: a100 mL Schlenk flask was selected, charged with the appropriate magnetons, and 48mg of Compound 3 and 91mg of DDQ were added to the flask, using a double calandria to evacuate the gas. Then 30mL of an anhydrous oxygen-free dichloromethane solution was added, the reaction system was placed at 0 ℃ and stirred for 5 minutes so that the entire reaction system reached 0 ℃, and then 1.5mL of methanesulfonic acid was added. The reaction was continued at 0 ℃ for 1 hour; finally adding hydrazine hydrate to quench the reaction. Diluting with dichloromethane, washing with water until the aqueous layer is colorless, collecting the organic layer, and collecting Na 2 SO 4 And (5) drying and spin-drying. The compound SNQ9H was unstable on silica gel column and the final target product was isolated using high performance liquid chromatography. The obtained SNQ9H had a clear mass spectrum as shown in fig. 5, a nuclear magnetic hydrogen spectrum as shown in fig. 6, and an X-ray single crystal diffraction characterization as shown in table 2 below. HRMS (LC-MALDI-TOF/TOF); m/z for C 164 H 95 NS 10 [M]calcd.2397.467,found:2397.473。
Table 2 table of X-ray crystallographic data for the donor material prepared in example three;
Figure BDA0003684734950000131
Figure BDA0003684734950000141
example four
The structural formula of the pentadiazo, thia [7] helicene (SNQ7H) donor material of this example is:
Figure BDA0003684734950000151
the synthetic route is as follows:
Figure BDA0003684734950000152
(1) synthesis of Compound 3: a25 mL Schlenk tube was selected,put the appropriate magneton into the flask, add 106mg of compound 1, 678mg of compound 2, 115mg of tetrakis (triphenylphosphine) palladium and 396mg of potassium carbonate, and pump the gas using a double calandria; then, 5mL of degassed N, N-dimethylformamide was injected into the reaction system, and reacted at 130 ℃ for 12 hours. The reaction was cooled to room temperature, extracted with dichloromethane and washed 3 times with water. The organic phase was collected, dried over Na2SO4 and spin dried. Separating and purifying by a silica gel chromatographic column, loading the sample by a dry method, and eluting by petroleum ether: dichloromethane ═ 3: 1. finally, 98mg of compound 3 were obtained, yield: 48 percent. 1 H NMR(400MHz,C 2 D 2 Cl 4 )δ＝7.54(m,16H),6.54(m,24H),2.22(m,75H).HRMS(LC-MALDI-TOF/TOF)；m/z for C 134 H 115 NS 10 [M]calcd.2057.624,found:2057.626。
(2) Compound SNQ 7H: selecting a 100mL Schlenk bottle, putting a proper magneton, weighing 50mg of compound 3 and 112mg of DDQ, putting the compound and the DDQ into the Schlenk bottle, and performing ventilation by using a double-calandria; then 30mL of an anhydrous oxygen-free dichloromethane solution was added, the reaction was stirred at 0 ℃ for 5 minutes, and then 1.5mL of methanesulfonic acid was added. The reaction was continued at 0 ℃ for 1 hour. Finally adding hydrazine hydrate for quenching, adding dichloromethane for diluting the reaction solution, washing with water until the water layer is colorless, collecting the organic layer, and adding Na 2 SO 4 And (5) drying and spin-drying. The compound SNQ7H was unstable on silica gel column and the final target product was isolated using high performance liquid chromatography. The SNQ7H obtained had a clear mass spectrum as shown in fig. 7, and an X-ray single crystal diffraction characterization as shown in table 3 below. HRMS (LC-MALDI-TOF/TOF); m/z for C 134 H 95 NS 10 [M]calcd.2037.467,found:2037.467。
Table 3 table of X-ray crystallographic data of donor material prepared in example four;
Figure BDA0003684734950000161
Figure BDA0003684734950000171
EXAMPLE five
The structural formula of the tris-diazo, thia [7] helicene (SNT7H) donor material of this example is:
Figure BDA0003684734950000172
the synthetic route is as follows:
Figure BDA0003684734950000173
(1) synthesis of Compound 3: selecting a 25mL Schlenk tube, putting a proper magneton, adding 93mg of compound 1, 678mg of compound 2, 115mg of tetrakis (triphenylphosphine) palladium and 396mg of potassium carbonate into the bottle, and using a double-row tube to pump air; subsequently, 5mL of degassed N, N-dimethylformamide was injected into the reaction system, and reacted at 130 ℃ for 12 hours. The reaction was cooled to room temperature, extracted with dichloromethane and washed 3 times with water. Collecting the organic phase, Na 2 SO 4 And (5) drying and spin-drying. Purifying and separating by silica gel chromatographic column, loading by dry method, and eluting with petroleum ether: dichloromethane ═ 3: 1. finally, 111mg of compound 3 was obtained, yield: 62 percent. 1 H NMR(400MHz,CD 2 Cl 2 )δ＝8.04(s,2H),8.03(s,2H),7.97(s,2H),7.95(s,2H),7.93(s,2H),7.68-7.53(m,8H),6.79-6.63(m,8H),5.98-5.61(m,8H),2.43(s,12H),1.87-1.99(s,12H),1.48(s,18H),1.45(s,18H),1.43(s,9H). 13 C NMR(100MHz,CD 2 Cl 2 )δ＝150.62,150.36,147.32,141.67,140.92,140.66,140.55,139.07,138.94,137.15,136.94,136.86,135.93,135.32,134.89,133.13,131.89,130.78,129.59,128.68,128.59,127.67,127.37,127.33,127.22,127.12,127.00,126.92,126.88,126.75,125.89,125.82,125.36,125.13,125.01,124.98,124.96,124.91,124.83,123.66,123.44,120.24,35.19,34.57,34.50,31.49,31.03,31.00,29.69,15.01,14.64.HRMS(LC-MALDI-TOF/TOF)；m/z for C 118 H 103 NS 8 [M]calcd.1789.585,found:1789.587。
(2) Synthesis of compound SNT 7H: selecting a 100mL Schlenk bottle, putting a proper magneton,add 50mg compound 3 and 126mg DDQ to the vial and use double calandria to pump the gas; 30mL of anhydrous oxygen-free dichloromethane solution were added, the reaction was placed at 0 ℃ and stirred for 5 minutes, followed by the addition of 1.5mL of methanesulfonic acid. The reaction was continued at 0 ℃ for 1 h. The reaction was finally quenched by addition of hydrazine hydrate, diluted with dichloromethane, washed with water until the aqueous layer was colorless, the organic layer was collected, dried over Na2SO4 and spin dried. The compound SNT7H is unstable on silica gel column, and the target product is separated by high performance liquid chromatography. The SNT7H obtained had a clear mass spectrum as shown in fig. 8, and an X-ray single crystal diffraction characterization as shown in table 4 below. HRMS (LC-MALDI-TOF/TOF); m/z for C 118 H 87 NS 8 [M]calcd.1773.460,found:1773.462。
Table 4 table of X-ray crystallographic data of donor materials prepared in example five;
Figure BDA0003684734950000181
Figure BDA0003684734950000191
EXAMPLE six
The pentadiazo and thia [9] spiroalkene SNQ9H electron donor material prepared in the third example is used for preparing organic solar cell devices and photovoltaic performance characterization thereof.
The preparation steps are as follows:
(1) the device structure is as follows: ITO/PEDOT PSS/SNQ9H PC 71 BM/PFNBr/Ag
(2) Ultrasonically cleaning an ITO conductive glass sheet for 1h by using a conductive glass cleaning agent, then ultrasonically cleaning the ITO conductive glass sheet for 1h by using absolute ethyl alcohol, then sequentially ultrasonically cleaning the ITO conductive glass sheet for 30min by using deionized water, ultrasonically cleaning the ITO conductive glass sheet for 15min by using acetone and ultrasonically cleaning the ITO conductive glass sheet for 15min by using isopropanol, and finally drying the ITO conductive glass sheet in an oven for later use;
(3) PSS was spin coated on ITO substrates at 3000rpm for 30s, and then annealed at 150 ℃ for 15min, transferring the samples into a glove box for use.
(4) At a mass ratio of 1:4SNQ9H and PC 71 BM was dissolved in chlorobenzene and stirred overnight to prepare a 25mg/mL mixed solution. The mixed solution was spin-coated on an ITO/PEDOT: PSS substrate at 2000rpm for 60s to prepare an active layer. The active layer was placed on a hot stage at 150 ℃ and annealed for 10 min.
(5) A1 mg/mL methanol solution of PFNBr was prepared and spun onto the active layer at 5000rpm for 30 s.
(6) And (3) plating silver electrodes of the battery prepared in the steps (1) to (5) to reach 100nm, wherein the effective area of the battery is 0.06cm 2.
The J-V curve of the organic solar cell prepared in the way is shown in figure 9, and the photovoltaic performance of the organic solar cell is as follows: open circuit voltage Voc 0.41V, short circuit current density Jsc 6.83mA/cm 2 The fill factor FF is 29.5%, and the photoelectric conversion efficiency PCE is 0.83%.
From the results, the spiroalkenyl electron donor material provided by the invention is a very potential organic solar cell electron donor material.
EXAMPLE seven
The preparation method of the tri-or penta-hetero [ n ] spiroalkene electron donor material shown in figure 1 comprises the following synthetic route:
Figure BDA0003684734950000201
wherein, R1-R2 are the same electron-donating groups respectively selected from H atom, aryl, hydroxyl, carbonyl, halogen atom or C1-10 straight-chain or branched alkyl group, C1-10 straight-chain or branched alkoxy group, C1-10 straight-chain or branched alkylthio group and C1-10 straight-chain or branched amine.
In the preparation method, the synthesis method of the compound B specifically comprises the following steps: taking a Schlenk bottle, carrying out anhydrous and anaerobic treatment, sequentially adding a compound A, an aromatic ring or aromatic ring combination connecting unit 2, a tetratriphenylphosphine palladium catalyst and potassium carbonate, replacing gas for 3 times, adding N, N-dimethylformamide under the protection of nitrogen to carry out Suzuki coupling reaction, and heating to the reaction temperature of 130 ℃. Reacting overnight, monitoring by TLC, cooling to room temperature, adding water, quenching, transferring the reaction stock solution to a separating funnel, extracting with dichloromethane, drying the organic phase with anhydrous sodium sulfate, performing rotary evaporation under reduced pressure, and separating with silica gel column using petroleum ether/dichloromethane as eluent to obtain yellow solid; the compound A, the aromatic ring or aromatic ring-fused connecting unit, the tetratriphenylphosphine palladium catalyst, the potassium carbonate and the N, N-dimethylformamide are mixed according to the proportion of 0.2-2 mmol, 2-20 mmol, 0.02-0.2 mmol, 3-15 mmol, 5-50 mL, the reaction temperature is 130 ℃, and the reaction time is 5-12 hours, specifically 5 hours or 12 hours.
The synthesis method of the compound C comprises the following steps: taking a Schlenk bottle, carrying out anhydrous anaerobic treatment, sequentially adding a compound B, dichlorodicyanoquinone (DDQ), trifluoromethanesulfonic acid or methanesulfonic acid as catalysts, displacing gas for 3 times, adding an anhydrous anaerobic dichloromethane solution under the protection of nitrogen to carry out Scholl reaction at the reaction temperature of 0 or 30 ℃; the reaction time is 0.5 or 4.5 h. After the reaction is finished, adding dichloromethane for dilution, adding water for extraction, collecting an organic phase, drying the organic phase by using anhydrous sodium sulfate, performing reduced pressure rotary evaporation on the solvent, and separating by using a High Performance Liquid Chromatography (HPLC); the chromatographic column for separation is a 5PBB column, a Bucky-M column or a 5PYE column. The green solution was obtained by separation and was black after spin drying. The compound B, DDQ, trifluoromethanesulfonic acid or methanesulfonic acid and dichloromethane are in the following ratio: 0.1 mmol-2 mmol-0.1 mL:20 mL.
In the embodiment, pentacene aza-cyclotene is adopted as a nucleus, firstly, pentacene aza-cyclotene is subjected to boron esterification to obtain a boron ester derivative thereof, then, polyterpene or the derivative and an electron-donating functional group are introduced through Suzuki-Miyaura coupling reaction, and finally, intramolecular oxidative dehydrogenation ring closure is performed through Scholl reaction; the introduced terphenyl or the derivative and the electron-donating functional group can effectively adjust the number of helices of molecules, change the size of a pi conjugated system of the molecules, improve the solubility of the molecules in an organic solvent and adjust the energy level of the molecules by introducing heteroatoms; the preparation process is simple and controllable, and the obtained electron donor material is applied to an organic solar cell, can improve the efficiency and stability of the organic solar cell, and is a potential organic solar cell electron donor material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. A tri-or penta-hetero [ n ] spiroalkene electron donor material characterized by: the electron donor material takes azacaryophyllene as an inner core, 4 or 5 aromatic ring pyrene structural units are symmetrically connected with the edge of the inner core, adjacent aromatic ring pyrene structural units and the edge of the inner core form single [ n ] helicene, and the single [ n ] helicene or the single [ n ] helicene and the single [ n ] helicene are contained together and have the following chemical structural formula:
Figure FDA0003684734940000011
wherein n is the number of ortho-position fused aromatic rings, m is the number of aromatic ring pyrene structural units, and Q is an aromatic ring or aromatic ring pyrene structural unit selected from aromatic rings and derivatives thereof; r1 and R2 are independently selected from any one of H atom, aryl group, amino group, halogen atom or C1-10 linear or branched alkyl group, C1-10 linear or branched alkoxy group, C1-10 linear or branched alkylthio group and C1-10 linear or branched amine.
2. A tri-or pentahetero [ n ] spiroene electron donor material according to claim 1, wherein: the chemical structural formula of Q is any one of the following:
Figure FDA0003684734940000021
wherein, X is any one of oxygen atom, sulfur atom, selenium atom or nitrogen atom; R1-R8 are independently selected from any one of H atom, aryl group, amino group, halogen atom or C1-10 linear or branched alkyl group, C1-10 linear or branched alkoxy group, C1-10 linear or branched alkylthio group and C1-10 linear or branched amine.
3. A quintuplex [7] spiroene electron donor material as claimed in any one of claims 1-2 wherein: when 5 benzopyrene structural units are symmetrically connected to the edge of the inner core, Q is phenyl, R1 is propoxy, R2 is H atom, and m is equal to 5, the electron donor material is an aza-penta [7] spiroalkenyl organic solar cell donor material, namely N-Q7H, and the chemical structural formula of the N-Q7H is as follows:
Figure FDA0003684734940000031
4. a quintuplex [9] spiroene electron donor material as claimed in any one of claims 1-2 wherein: when the edge of the inner core is symmetrically connected with 5 structural units of aromatic ring pyrene, Q is naphthyl, R1 is dimethyl-phenyl, R2 is tert-butyl, and m is equal to 5, the electron donor material is an aza-penta [9] spiroalkene-based organic solar cell donor material, namely N-Q9H, and the chemical structural formula of the N-Q9H is as follows:
Figure FDA0003684734940000032
5. a pentadiazo, thia [9] spiroene electron donor material as claimed in any one of claims 1-2 wherein: when the edge of the inner core is symmetrically connected with 5 structural units of aromatic ring pyrene, Q is benzothiophene, R1 is H atom, R2 is tert-butyl, and m is equal to 5, the electron donor material is a sulfur and aza-penta [9] spiroalkene-based organic solar cell donor material, namely SNQ9H, and the chemical structural formula of the SNQ9H is as follows:
Figure FDA0003684734940000041
6. a pentadiazo, thia [7] spiroene electron donor material as claimed in any one of claims 1-2 wherein: when the edge of the inner core is symmetrically connected with 5 structural units of aromatic ring pyrene, Q is thiophene, R1 is methyl, R2 is tert-butyl, and m is equal to 5, the electron donor material is a sulfur and aza-penta [7] spiroalkene-based organic solar cell donor material, namely SNQ7H, and the chemical structural formula of the SNQ7H is as follows:
Figure FDA0003684734940000042
7. a triple nitrogen, thia [7] helicene electron donor material according to any of claims 1-2, wherein: when 4 structural units of aromatic ring pyrene are symmetrically connected to the edge of the inner core, Q is thiophene, R1 is methyl, R2 is tert-butyl, and m is equal to 4, the electron donor material is a sulfur and aza-triplet [7] spiroalkenyl organic solar cell donor material, namely SNT7H, and the chemical structural formula of the SNT7H is as follows:
Figure FDA0003684734940000051
8. a process for the preparation of a tri-or pentahetero [ n ] spiroalkene electron donor material according to claim 1, characterized in that: the method comprises the following steps:
s1, carrying out carbon-hydrogen bond boronization on pentabenzoazacarylene and bisphenopinacol borate under the action of an iridium catalyst to obtain a pentabenzoazacarylene-pentaborate and a pentabenzoazacarylene-tetraboroborate reaction synthon;
s2, dissolving the tetra-or pentaboron ester compound of pentabenzo-aza-caryophyllene and iodo terphenyl or derivatives in an organic solvent at 130 ℃, heating and reacting for 12h under the action of alkali and palladium catalyst, performing Suzuki-Miyaura coupling reaction, and performing intramolecular dehydrocyclization reaction through Scholl reaction to obtain tri-or penta-hetero [ n ] spiroalkene molecules used as donor materials of the organic solar cell.
9. A process for the preparation of a tri-or pentahetero [ n ] spiroalkene electron donor material according to claim 8, characterized in that: the base adopted in the Suzuki-Miyaura coupling reaction is any one or more of potassium carbonate, potassium phosphate and cesium carbonate; the organic solvent adopted in the Suzuki-Miyaura coupling reaction is N, N-dimethylformamide.
10. Use of a tri-or pentahetero [ n ] spiroalkene electron donor material according to claim 1, characterized in that: the electron donor material is applied to an organic solar cell.
CN202210647969.2A 2022-06-08 2022-06-08 Tri-or quintuple hetero [ n ] spiroalkene electron donor material and preparation method and application thereof Pending CN114920742A (en)

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CN112979611A (en) * 2021-02-07 2021-06-18 厦门大学 Bowl alkenyl perovskite solar cell hole transport layer material and preparation method and application thereof

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