CN108191917B - Automatic-regulation photoelectric conversion molecule and preparation method thereof - Google Patents

Automatic-regulation photoelectric conversion molecule and preparation method thereof Download PDF

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CN108191917B
CN108191917B CN201810018270.3A CN201810018270A CN108191917B CN 108191917 B CN108191917 B CN 108191917B CN 201810018270 A CN201810018270 A CN 201810018270A CN 108191917 B CN108191917 B CN 108191917B
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electron
photoelectric conversion
photoswitch
molecules
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CN108191917A (en
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江俊
伍子夜
罗毅
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Hefei Jiqian Quantum Technology Co ltd
Jiang Jun
Luo Yi
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University of Science and Technology of China USTC
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    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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Abstract

The invention provides an automatically regulated photoelectric conversion molecule, which comprises: an optical switch molecule; an electron donor covalently linked to one end of the photoswitch molecule; an electron acceptor linked to the other end of the photoswitch molecule through an acetylene group; the photoswitch molecule is a group comprising a photochromic compound; the electron donor is a group capable of providing an electron; the electron acceptor is a group having an electron accepting ability and having a stronger electronegativity than the electron donor and the photoswitch molecule. The automatically regulated photoelectric conversion molecules can efficiently collect solar energy and convert the solar energy into excited state electron energy. The initial structure is an 'open' structure, electrons are transferred from a donor and an optical switch to a receptor under illumination, the optical switch is triggered to be automatically closed, the flow of charges in molecules is blocked, stimulated electrons cannot be subjected to backflow recombination, and the efficient separation of the charges in an organic molecular system is realized; and the closed optical switch absorbs light and is switched back to the open state after the excited electrons are consumed, so that automatic circulation is realized.

Description

Automatic-regulation photoelectric conversion molecule and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric conversion and new energy materials, in particular to an automatically regulated photoelectric conversion molecule and a preparation method thereof.
Background
With the decrease of traditional energy fuel, the pollution to the environment is becoming more serious, and the energy problem becomes an important factor which troubles the development of human beings. Compared with the use of fossil fuel, solar energy is an inexhaustible pollution-free energy source and has incomparable advantages. Currently, there are three general ways of utilizing solar energy: (1) converting solar energy into electric energy, namely photoelectric conversion; (2) converting solar energy into heat energy, namely photo-thermal conversion; (3) solar energy is converted into chemical energy, i.e. photochemical conversion. Solar cells, which have been rapidly developed in recent years, convert solar energy into electric energy by photoelectric conversion.
The organic solar cell uses a conjugated structure organic matter with photosensitive property as a material, and generates voltage by photovoltaic effect so as to form current. Compared with the currently used solar cell materials such as silicon and the like, the organic solar cell material has the advantages of wide source, low price, simple preparation process, good flexibility, easy large-scale production, light weight, softness, easy carrying, degradability and small environmental pollution, and has better development potential from the current development trend. However, the photoelectric conversion efficiency of the organic solar cell reported at present is only 11.5% at most, and the difference is still large compared with that of a semiconductor solar cell. This is because the charge which is not completely separated is easily recombined due to the low carrier mobility of the organic molecules, thereby greatly limiting the improvement of the photoelectric efficiency.
Organic solar cells can be classified into three types according to their structures, wherein p-n heterojunction organic solar cells have a donor (D) -acceptor (a) structure, the exciton separation efficiency is improved due to the presence of a D/a interface, and the efficiency may be further improved by adding some specific structures between D and a. Castellanos et al found that the charge recombination rate of a non-conducting molecule between a donor and an acceptor is much lower than that of a conducting molecule, but the design cannot realize the switching of conductivity, and the conducting and non-conducting conditions correspond to two independent systems respectively, so that in the non-conducting system, although the charge recombination is inhibited, the charge transfer may be inhibited, and the photoelectric conversion efficiency is reduced. Therefore, in order to actually improve the photoelectric conversion efficiency of the organic solar cell, it is necessary to design a system capable of simultaneously realizing efficient charge transfer and thorough charge separation.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an auto-adjusting photoelectric conversion molecule and a method for preparing the same, which can realize efficient charge transfer under illumination conditions and realize charge separation by auto-adjusting configuration.
In order to solve the above technical problems, the present invention provides an automatically regulated photoelectric conversion molecule, comprising:
an optical switch molecule;
and an electron donor covalently linked to one end of the photoswitch molecule;
and an electron acceptor linked to the other end of the photoswitch molecule through an ethynyl group;
the photoswitch molecule is a group comprising a photochromic compound;
the electron donor is a group capable of providing an electron;
the electron acceptor is a group having an electron accepting ability and having a stronger electronegativity than the electron donor and the photoswitch molecule.
The invention forms A D-S-A structure through optical switch molecules, electron donors and electron acceptors.
Among the optical switch molecules, the optical switch molecules with the 'on' configuration have a conjugated structure and good conductivity, and the conjugated structure of the molecules with the 'off' configuration is damaged and poor conductivity; when the photoswitch molecules lose electrons, the switching barrier will decrease and the molecules will spontaneously switch from the "on" configuration to the "off" configuration.
Wherein the optical switch molecule is a group comprising a photochromic compound. Specifically, two hydrogen atoms or residues of substituents are missing for the photochromic compound. The photochromic compound can be a photochromic compound known in the art, and can change a chemical structure under illumination of specific wavelength to generate a product with a novel structure, and the product can restore to the original structure under the action of light radiation of another wavelength or heat.
The structural changes comprise heterolytic cleavage of ① bonds, such as spiropyran, spirooxazine and the like, homolytic cleavage of ② bonds, such as hexaphenylbisimidazole, tetrachloronaphthalene derivatives and the like, ③ proton transfer tautomerism, such as salicylaldehyde aniline compounds and the like, ④ cis-trans isomerism, such as styrenes, benzylidene anilines, azo compounds and the like, ⑤ redox reactions, such as fused ring aromatic compounds and the like, ⑥ cyclocyclization reactions, such as fulgides, diarylethene compounds and the like, ⑦ aryl migration reactions, such as phenoxynaphthaquinone and the like.
Preferably, the photochromic compound is azobenzene, spiropyran, spirooxazine, fulgide, naphthonaphthoquinone, naphthopyran, N-o-hydroxybenzylideneaniline, dimethyldihydropyrene or diarylethene photochromic compound, or derivatives thereof.
The derivative may be one in which a general substituent, such as C1 to C3 alkyl (e.g., methyl, ethyl, propyl, isopropyl), C1 to C3 alkoxy (e.g., methoxy, ethoxy, propoxy, isopropoxy), phenyl, carbonyl, aldehyde, cyano, hydroxyl, halogen, carboxyl, nitro, sulfonic acid, amino, acyl, amide, or the like, is introduced into an aryl group or a functional group.
The diarylethene photochromic compound is preferably stilbene, dithiophene pentene or dithiophene ethylene.
The source of the optical switch molecule in the present invention is not particularly limited, and it may be generally commercially available or prepared by a method known to those skilled in the art. Taking 4, 4' -diiodoazobenzene as an example, the preparation method can be realized according to the following method:
I) dissolving aniline and sodium bicarbonate in water, adding iodine while stirring, continuously stirring, filtering, and recrystallizing to obtain p-iodoaniline crystals;
II), dissolving the p-iodoaniline crystal, potassium permanganate and copper sulfate pentahydrate, stirring, refluxing, filtering and purifying to obtain a 4, 4' -diiodoazobenzene solid.
In the preparation method provided by the invention, the stirring time in the step I) is preferably 1-2 h; the solvents used for the recrystallization in step I) are preferably absolute ethanol and petroleum ether. The dissolved solvent in step II) is preferably dichloromethane and/or trichloromethane; the stirring time in the step II) is preferably 2-3 d; the purification in step II) is preferably carried out by drying over anhydrous magnesium sulfate, then distilling off the solvent under reduced pressure, and then purifying by column chromatography (petroleum ether: ethyl acetate 6: 1).
In the present invention, the electron donor is linked to one end of the photoswitch molecule by a covalent bond, which is preferably a group capable of providing an electron.
The electron donor is preferably olefin compounds, alkyne compounds, alicyclic hydrocarbon compounds, aromatic hydrocarbon compounds or heterocyclic compounds, or polymers and derivatives of the above compounds, or copolymers and derivatives thereof obtained by any combination of the above compounds.
Preferably, the olefin compound is ethylene or propylene; the alkyne compound is acetylene or propyne; the alicyclic hydrocarbon compound is cyclopropene, cyclobutene, cyclopentene, cyclohexene or annulene; the aromatic hydrocarbon compound is benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, indene, acenaphthene, fluorene,
Figure BDA0001542695140000031
Fluoranthene or benzyne; the heterocyclic compound is thiophene, pyrrole, furan, carbazole, porphyrin, pyridine, pyrimidine, quinoline, imidazole, indole, pyrazine, pteridine or acridine.
The derivative may be one in which a general substituent is introduced into the above compound, such as C1 to C3 alkyl (e.g., methyl, ethyl, propyl, isopropyl), C1 to C3 alkoxy (e.g., methoxy, ethoxy, propoxy, isopropoxy), phenyl, carbonyl, aldehyde, cyano, hydroxyl, halogen, carboxyl, nitro, sulfonic acid, amino, acyl, amide, and the like.
In particular, the electron donor is the residue of the above compound, which has lost one hydrogen atom or substituent.
In certain embodiments of the present invention, the electron donor is phenylacetylene, 1-ethynyl-4- (phenylethynyl) benzene, or 1-ethynyl-4- ((4- (phenylethynyl) phenyl) ethynyl) benzene.
The source of the electron donor in the present invention is not particularly limited, and the electron donor may be commercially available or may be prepared by a method known to those skilled in the art, and the monomer phenylacetylene may be prepared by the following method:
i) adding styrene into carbon tetrachloride, dripping bromine into a carbon tetrachloride solution under stirring, continuously stirring for reaction, and filtering to obtain dibromophenylethane solid;
ii) adding the dibromophenylethane solid into methanol, adding potassium hydroxide, heating for reflux reaction, and cooling to obtain a reaction solution;
and iii) filtering the reaction liquid, extracting filtrate, and distilling to obtain phenylacetylene liquid.
In the preparation method provided by the invention, the temperature of the bromine-added carbon tetrachloride solution stirred in the step i) is preferably 5-15 ℃; the stirring reaction time in the step i) is preferably 30-60 min. The heating reflux time in the step ii) is preferably 1-2 h. The extraction in step iii) is preferably carried out by using diethyl ether, and the upper solution is collected; the distillation in step iii) is preferably carried out by atmospheric distillation followed by vacuum distillation.
In the present invention, the electron acceptor is connected to the other end of the photoswitch molecule through an acetylene group, and is preferably a group having an electron accepting ability and having a stronger electronegativity than the electron donor and the photoswitch molecule.
The electron acceptor is preferably terpyridine platinum complex, perylene imide, rhodamine, oxadiazole, benzothiazole, o-oxonone, fullerene, porphyrin, pyridine, pyrimidine, quinoline and quinoxaline, or aryl with electron-withdrawing groups, or derivatives of the above compounds.
The electron withdrawing group is preferably one or more of halogen, nitro, cyano, carbonyl, acyl, carboxyl and sulfonic acid.
The derivative may be one in which a general substituent is introduced into the above compound, such as C1 to C3 alkyl (e.g., methyl, ethyl, propyl, isopropyl), C1 to C3 alkoxy (e.g., methoxy, ethoxy, propoxy, isopropoxy), phenyl, carbonyl, aldehyde, cyano, hydroxyl, halogen, carboxyl, nitro, sulfonic acid, amino, acyl, amide, and the like.
Specifically, the electron acceptor is a residue of the above compound having one hydrogen atom or substituent removed.
In certain embodiments of the invention, the electron acceptor is 2,2 ', 6 ', 2 "-terpyridoplatin, 4 ', 4" -tri-tert-butyl-2, 2 ', 6 ', 2 "-terpyridoplatin, and 4-phenyl-2, 2 ', 6 ', 2" -terpyridoplatin.
The electron acceptor of the present invention is not particularly limited in its source, and may be commercially available or prepared by a method known to those skilled in the art, and for example, 4-phenyl-2, 2 ', 6', 2 ″ -terpyridine platinum chloride complex can be prepared by the following method:
s1), dissolving diacetyl pyridine and benzaldehyde in ethanol, adding a sodium hydroxide solution, and stirring to obtain a mixed solution;
s2), adding an ethanol solution of ammonium acetate into the mixed solution, stirring at normal temperature until a solid is generated, adding a large amount of water until no precipitate is separated out, carrying out suction filtration and washing on a crude product, then drying with anhydrous magnesium sulfate, and recrystallizing with ethanol to obtain a 4-phenyl terpyridine crystal;
s3), dissolving the 4-phenyl terpyridine crystals in hot acetonitrile, and slowly adding K thereto2PtCl4Heating the aqueous solution, carrying out reflux reaction, cooling and carrying out suction filtration to obtain a crude product;
s4) to obtain 4-phenyl-2, 2 ', 6 ', 2 ' -terpyridine platinum chloride complex solid after washing and drying.
In the above preparation method provided by the present invention, the stirring time in step s1) is preferably 30 min. The stirring time in step s2) is preferably 3 d; the washing in step s2) is preferably carried out with dichloromethane and saturated sodium bicarbonate, respectively. The 4-phenyl terpyridine crystals and K in step s3)2PtCl4Is preferably 1: 1; the reflux reaction time in step s3) is preferably 24 h. The washing manner described in step s4) preferably comprises washing with water, dichloromethane, diethyl ether in sequence.
In the present invention, the electron donor and the electron acceptor are relative concepts, and there is no definite limit between them, and when there is electron transfer in the system, the electron donor is the electron donor, and the electron acceptor is the electron acceptor.
The invention also provides a preparation method of the automatic-regulation photoelectric conversion molecule, which comprises the following steps:
A) reacting the photoswitch molecules with an electron donor compound and acetylene in tetrahydrofuran under the action of a catalyst to obtain photoswitch molecules, wherein one end of each photoswitch molecule is substituted by an electron donor, and the other end of each photoswitch molecule is substituted by acetylene;
B) dissolving the photoswitch molecule obtained in the step A) and an electron acceptor compound in dichloromethane, reacting under the action of a catalyst, purifying a crude product by column chromatography, and recrystallizing to obtain the automatically-controlled photoelectric conversion molecule.
In the above step a), the molar ratio of the photoswitch molecule, the electron donor compound, and acetylene is preferably 1:1: 1.
The photoswitch molecules preferably have halogen substituents. More preferably a bromine substituent.
The catalyst is preferably bis triphenylphosphine palladium dichloride and cuprous iodide.
The reaction is carried out under the action of N, N-diisophenylethylamine.
The reaction is preferably carried out under the protection of nitrogen, the temperature of the reaction is preferably 50 ℃, and the time of the reaction is preferably 20-50 h.
In the step B), the catalyst is preferably cuprous iodide, and the reaction is preferably carried out under the action of diisopropylamine.
The electron acceptor compounds preferably bear halogen substituents. More preferably a bromine substituent.
The reaction is preferably carried out in an inert argon atmosphere, the reaction temperature is preferably 20-30 ℃, and the reaction time is preferably 17-24 h.
The method takes the example that the optical switch molecule is 4, 4' -diiodoazobenzene, the electron donor is phenylacetylene, and the electron acceptor is a terpyridyl platinum complex, and concretely comprises the following steps:
a1) reacting 4, 4' -diiodo azobenzene with phenylacetylene and acetylene in tetrahydrofuran under the action of a catalyst to obtain an azobenzene molecule with one end substituted by phenylacetylene and the other end substituted by acetylene;
a2) and dissolving the azobenzene molecules with the substituted two ends obtained in the step a1) and the terpyridyl platinum complex in dichloromethane, reacting under the action of a catalyst, purifying a crude product by column chromatography, and recrystallizing to obtain the crystal of the photoelectric conversion molecule.
Specifically, 4' -diiodoazobenzene is dissolved in tetrahydrofuran, N-diisophenylethylamine and catalysts of bis (triphenylphosphine) palladium dichloride and cuprous iodide are added, and the mixture is stirred for 30min at 50 ℃ under the protection of nitrogen. Then adding phenylacetylene and acetylene, reacting for 24 hours, adding water to quench the reaction, and extracting with trichloromethane to obtain a crude product. Wherein the molar ratio of the 4, 4' -diiodoazobenzene to the phenylacetylene to the acetylene is 1:1: 1. Drying the crude product with anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating and purifying by column chromatography, and recrystallizing with dichloromethane and ethanol to obtain the product.
And after obtaining a product, dissolving the product and a terpyridyl platinum complex in dichloromethane, adding diisopropylamine and a catalyst cuprous iodide, and stirring at room temperature in a dark place under an inert argon atmosphere for reacting for 17-24h to obtain a crude product. And purifying the crude product by column chromatography to obtain the photoelectric conversion molecular solid.
The invention also provides another method for preparing the automatic-regulation photoelectric conversion molecule, which comprises the following steps:
a') dissolving photoswitch molecules with one end substituted by an electron donor and the other end substituted by acetylene and potassium hydroxide in anhydrous methanol, and stirring to obtain a mixed solution;
b') adding an electron acceptor compound and cuprous iodide into the mixed solution, stirring for reaction, and purifying to obtain the automatically regulated photoelectric conversion molecules.
The preparation method of the optical switch molecule with one end substituted by the electron donor and the other end substituted by acetylene is the same as above, and is not described again here.
Firstly, dissolving optical switch molecules with two substituted ends and potassium hydroxide in absolute methanol, and stirring at normal temperature to obtain a mixed solution. The stirring time is preferably 30 min.
And after the mixed solution is obtained, adding an electron acceptor compound and a catalyst cuprous iodide into the mixed solution, and stirring for reaction to obtain a reaction solution. The stirring reaction is preferably carried out under the condition of keeping out of the light, the stirring time is preferably 24 hours, and the stirring temperature is preferably room temperature.
The purification is preferably to filter the reaction solution, wash the filter cake with dichloromethane and water respectively, then dissolve the filter cake with methanol, add ammonium hexafluorophosphate, stir for 3h at normal temperature, filter and wash to obtain the photoelectric conversion molecular solid.
The automatically regulated photoelectric conversion molecule provided by the invention has the following properties:
under the illumination condition, electrons are transferred in the photoelectric conversion molecules; the transferred electrons can not be subjected to backflow recombination due to configuration conversion of the optical switch, so that charge separation is realized; until the excited electrons are consumed, the photoswitch molecules absorb photons and convert back to the initial configuration, and automatic circulation is realized.
Specifically, the optical switch molecules in the photoelectric conversion molecules, the electron donor and the electron acceptor are in a covalent bond mode, the optical switch molecules are positioned between the electron donor and the electron acceptor, and an ethynyl group is added between the optical switch molecules and the electron acceptor for ensuring conjugation, so that the whole molecules are in a conjugated planar structure and have strong electrical conductivity; and the composite material has good light absorption capacity in the visible light range of solar energy, and can efficiently collect solar energy, so that the composite material is suitable for the field of monomolecular photoelectronic devices. On the other hand, energy level structure differences exist among the optical switch, the donor and the acceptor in the molecule, the molecule absorbs photon energy and then generates electron transfer, and photo-generated electrons are transferred from the optical switch and the donor to the acceptor; by utilizing the characteristics of switch conversion barrier reduction after the switch molecules lose electrons and configuration conversion after light absorption, the photoelectric conversion molecules can trigger the optical switch to be automatically closed after the photo-excited electrons are transferred, the molecular conjugated structure is damaged, the conductivity is poor, the photo-generated electrons cannot be reflowed and compounded, so that the photo-generated electrons are stored in the acceptor, and the corresponding holes are reserved in the donor and the optical switch, so that efficient charge separation is realized; until the electrons in the acceptor are consumed, the molecules return to the ground state ("off" configuration) from the excited state, and the optical switch in the ground state absorbs visible light and switches back to the initial "on" configuration, so that the automatic cycle is realized, and therefore, the photoelectric conversion is also suitable for the field of solar cells.
The working mechanism of the photoelectric conversion molecule for realizing charge separation and automatic circulation provided by the invention is as follows: (1) the photoelectric conversion molecules in the "on" configuration generate excited electrons by absorbing visible light; (2) excited electrons are rapidly transferred from the photoswitch and the electron donor to an acceptor with lower energy level, and the photoswitch and the electron donor are positively charged due to the loss of electrons; (3) the configuration conversion barrier of the optical switch losing electrons is lowered, and the optical switch spontaneously converts from an 'on' configuration to an 'off' configuration; (4) the molecule conjugated structure is destroyed, the excited electron on the acceptor can not return to the photoswitch and the donor, so that the electron and the hole are respectively stored on the acceptor and the donor-photoswitch, and the charge separation is realized; (5) after the excited electrons are utilized or consumed, the molecule returns from the excited state to the ground state in the "off" configuration; (6) due to the nature of the photoswitch molecule, a molecule in the ground state in the "off" configuration will absorb visible light back to the "on" configuration.
Compared with the prior art, the invention provides an automatically regulated photoelectric conversion molecule, which comprises: an optical switch molecule; and an electron donor covalently linked to one end of the photoswitch molecule; and an electron acceptor linked to the other end of the photoswitch molecule through an ethynyl group; the photoswitch molecule is a group comprising a photochromic compound; the electron donor is a group capable of providing an electron; the electron acceptor is a group having an electron accepting ability and having a stronger electronegativity than the electron donor and the photoswitch molecule.
The automatically regulated photoelectric conversion molecule skillfully utilizes the characteristics of switch conversion barrier reduction after electron loss of the switch molecule and configuration conversion after light absorption, triggers the automatic closing of the optical switch after the transfer of light-excited electrons, ensures that the basic state molecules of the off configuration can automatically return to the on configuration after the consumption of the excited electrons and the light absorption, and realizes charge separation and automatic circulation through the automatic switching of the molecular configuration. Organic micromolecules are adopted as materials, so that the cost is low, the preparation process is simple, and the large-scale production is easy. The problem of low photoelectric conversion efficiency caused by charge recombination easily occurring in an organic solar cell is solved, the problem that the conductivity cannot be switched in a common system is solved, and a new way is opened up for the concept design and the practical application of realizing high-efficiency photoelectric conversion.
The system is suitable for the fields of monomolecular photoelectronic devices and solar cells, and opens up a new way for realizing the design and the practical application of converting solar energy into electric energy efficiently.
Drawings
FIG. 1 is a drawing showing a drawing of a document D according to an embodiment of the present invention1-azo-AtBu3Optimal stable configuration of the molecule;
FIG. 2 shows trans-azo, D provided by an embodiment of the present invention1-AtBu3And D1-azo-AtBu3Ultraviolet-visible absorption spectrum of the molecule;
FIG. 3 is a drawing showing a step D according to an embodiment of the present inventionn-azo-AtBu3(n-3, 5,7) ultraviolet-visible absorption spectrum of molecule;
FIG. 4 is a drawing showing a step D according to an embodiment of the present invention1-azo-AtBu3A molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state;
FIG. 5 is a drawing showing a step D according to an embodiment of the present invention3-azo-AtBu3A molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state;
FIG. 6 shows a schematic diagram of a block diagram D5-azo-AtBu3A molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state;
FIG. 7 is a drawing showing a step D according to an embodiment of the present invention7-azo-AtBu3A molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state;
FIG. 8 is a graph of the configuration transition potential of azobenzene (azo) molecules according to an embodiment of the present invention;
FIG. 9 is a graph showing the configuration transition potential of an N-o-hydroxybenzylideneaniline molecule according to an embodiment of the present invention;
FIG. 10 is a graph of the configuration transition potential of a1, 2-bis (2, 5-dimethyl-3-thienyl) perfluorocyclopentene molecule according to an embodiment of the present invention;
FIG. 11 is a graph of the configuration transition potential of a1, 2-bis (3, 5-dimethyl-2-thienyl) perfluorocyclopentene molecule according to an embodiment of the present invention;
FIG. 12 is a graph of the configuration transformation potential energy of a dimethyldihydropyrene derivative molecule provided by an embodiment of the present invention;
FIG. 13 is a drawing showing a step D according to an embodiment of the present invention1-azo-AtBu3Configuration of a first excited state of the molecule;
FIG. 14 is a drawing showing a step D according to an embodiment of the present invention1-azo-AtBu3A molecular orbital wave function corresponding to a molecular first excited state radiation transition;
FIG. 15 is a drawing showing a step D according to an embodiment of the present invention1-azo-AtBu3Electron tunneling spectra in the molecular "on" and "off configurations;
FIG. 16 is a drawing showing a step D according to an embodiment of the present invention1-azo-AtBu3Electron evolution profiles of the "on" and "off" configurations of the molecule;
FIG. 17 is a representation of cis azo and "off configuration D as provided by an embodiment of the present invention1-azo-AtBu3Ultraviolet-visible absorption spectrum of the molecule;
FIG. 18 shows cis azo and "off configuration D as provided by an embodiment of the present invention1-azo-AtBu3And (3) the molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state.
Detailed Description
In order to further illustrate the present invention, the following examples are given to describe the self-regulating photoelectric conversion molecule and the preparation method thereof in detail.
Example 1
Preparation of 4, 4' -diiodoazobenzene (I-azo-I):
(1) aniline is used as a precursor and is placed into a four-neck flask, after the aniline is fully stirred, powdered iodine is slowly added in batches within 30min, and stirring is continued for 30min until the reaction is finished;
(2) adding saturated NaHSO into the reaction solution3Stirring and filtering the solution, and recrystallizing the obtained solid with petroleum ether to obtain p-iodoaniline crystals;
(3) adding p-iodoaniline, potassium permanganate, copper sulfate pentahydrate and chloroform into a round-bottom flask, and stirring and refluxing for 48 hours until the reaction is finished;
(4) filtering, washing the reaction residue with saturated sodium thiosulfate solution, brine and water in turn, evaporating the solvent under reduced pressure, and purifying by column chromatography (eluent: petroleum ether/ethyl acetate: 6/1) to obtain 4, 4' -diiodoazobenzene as a solid.
Example 2
Preparation of phenylacetylene (D)1)：
(1) Adding styrene and CCl into a three-mouth bottle4Stirring uniformly, cooling to 5-15 ℃, and slowly dripping Br while stirring2CCl of (2)4Continuously stirring the solution for reaction for 30-60 min, and filtering to obtain dibromophenylethane solid;
(2) dibromophenylethane solid, KOH and CH3And adding OH into a three-necked bottle, heating and refluxing for reaction for 1-2 h, cooling, filtering, extracting filtrate with diethyl ether, collecting an upper layer solution, distilling at normal pressure, and then distilling and purifying at reduced pressure to obtain phenylacetylene liquid.
Example 3
Preparation of 4-phenyl-2, 2 ', 6', 2 "-terpyridine platinum chloride complex (APh-Cl):
(1) dissolving diacetyl pyridine and benzaldehyde in ethanol, adding a NaOH solution, stirring for 30min, adding an ethanol solution of ammonium acetate, stirring for 3d at normal temperature until no precipitate is separated out, generating a solid, adding a large amount of water, performing suction filtration, washing a filter cake with dichloromethane and saturated sodium bicarbonate respectively, drying with anhydrous magnesium sulfate, and recrystallizing with ethanol to obtain a 4-phenyl terpyridine crystal;
(2) 4-phenyl terpyridine crystals are dissolved in hot acetonitrile, to which K is slowly added2PtCl4Heating the aqueous solution, and carrying out reflux reaction for 24 hours until the reaction is finished;
(3) and cooling the reaction liquid, performing suction filtration, washing a filter cake with water, dichloromethane and diethyl ether in sequence, and drying to obtain the 4-phenyl-2, 2 ', 6 ', 2 ' -terpyridyl platinum chloride complex solid.
Example 4
Preparation of photoelectric conversion molecule (D)1-azo-APh)：
The 4, 4' -diiodoazobenzene prepared in example 1 was dissolved in tetrahydrofuran, and N, N-diisophenylethylamine and a catalyst bis triphenylphosphine palladium dichloride/cuprous iodide were added and stirred at 50 ℃ for 30min under nitrogen protection. Acetylene and the phenylacetylene prepared in example 2 were then added, and after 24 hours of reaction, water was added to quench the reaction, which was extracted with chloroform to give a crude product. Wherein the molar ratio of the 4, 4' -diiodoazobenzene to the phenylacetylene to the acetylene is 1:1: 1. Drying the crude product with anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating and purifying by column chromatography, and recrystallizing with dichloromethane and ethanol to obtain azobenzene molecules with two ends respectively substituted by phenylacetylene and acetylene.
And (3) dissolving azobenzene with two ends respectively substituted by phenylacetylene and acetylene and the APh-Cl complex prepared in the embodiment 3 in dichloromethane, adding diisopropylamine and cuprous iodide serving as a catalyst, and stirring and reacting at room temperature in a dark place under an inert argon atmosphere for 17-24 hours to obtain a crude product. And purifying the crude product by column chromatography to obtain the photoelectric conversion molecular solid.
Referring to the method provided in this example, the corresponding photoelectric conversion molecule can be prepared by replacing 4,4 '-diiodoazobenzene with spiropyran, spirooxazine, fulgide, naphthonaphthoquinone, naphthopyran, N-o-hydroxybenzylideneaniline, dimethyldihydropyrene, stilbene, dithiophene, dithiophenethylene, phenylacetylene with 1-ethynyl-4- (phenylethynyl) benzene or 1-ethynyl-4- ((4- (phenylethynyl) phenyl) ethynyl) benzene, and 4-phenyl-2, 2', 6 ', 2 "-terpicoliplatin with 2, 2', 6 ', 2" -terpicoliplatin or 4, 4', 4 "-tri-tert-butyl-2, 2 ', 6', 2" -terpicolinatin.
Example 5
Preparation of photoelectric conversion molecule (D)1-azo-APh)：
The 4, 4' -diiodoazobenzene prepared in example 1 was dissolved in tetrahydrofuran, and N, N-diisophenylethylamine and a catalyst bis triphenylphosphine palladium dichloride/cuprous iodide were added and stirred at 50 ℃ for 30min under nitrogen protection. Acetylene and the phenylacetylene prepared in example 2 were then added, and after 24 hours of reaction, water was added to quench the reaction, which was extracted with chloroform to give a crude product. Wherein the molar ratio of the 4, 4' -diiodoazobenzene to the phenylacetylene to the acetylene is 1:1: 1. Drying the crude product with anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, separating and purifying by column chromatography, and recrystallizing with dichloromethane and ethanol to obtain azobenzene molecules with two ends respectively substituted by phenylacetylene and acetylene.
Azobenzene and potassium hydroxide, both ends of which are respectively substituted by phenylacetylene and acetylene, are dissolved in absolute methanol, stirred for 30min at normal temperature, the 4-phenyl-2, 2 ': 6 ', 2 ' -terpyridyl platinum chloride complex prepared in example 3 and cuprous iodide serving as a catalyst are added into the solution, and stirred for 24h at normal temperature in a dark place to obtain a reaction solution. And filtering the reaction solution, washing the filter cake with dichloromethane and water respectively, dissolving the filter cake with methanol, adding ammonium hexafluorophosphate, stirring at normal temperature for 3 hours, filtering and washing to obtain the photoelectric conversion molecular solid.
Referring to the method provided in this example, the corresponding photoelectric conversion molecule can be prepared by replacing 4,4 '-diiodoazobenzene with spiropyran, spirooxazine, fulgide, naphthonaphthoquinone, naphthopyran, N-o-hydroxybenzylideneaniline, dimethyldihydropyrene, stilbene, dithiophene, dithiophenethylene, phenylacetylene with 1-ethynyl-4- (phenylethynyl) benzene or 1-ethynyl-4- ((4- (phenylethynyl) phenyl) ethynyl) benzene, and 4-phenyl-2, 2', 6 ', 2 "-terpicoliplatin with 2, 2', 6 ', 2" -terpicoliplatin or 4, 4', 4 "-tri-tert-butyl-2, 2 ', 6', 2" -terpicolinatin.
Example 6
And (3) performance detection: constructing an initial configuration through Gauss View, performing structural optimization by using a Gaussian09 software package, and verifying that the optimal configuration of the photoelectric conversion molecule 'on' configuration is a conjugated planar structure; based on the stable configuration, calculating the optical property, excited state property and the like of the molecule, and confirming the efficient light absorption performance and electron transfer capability of the photoelectric conversion molecule; calculating a potential energy curve of the optical switch molecular configuration conversion, analyzing the change of a conversion potential barrier after the optical switch molecular configuration conversion loses electrons, optimizing the excited state configuration of the photoelectric conversion molecule, and confirming that the molecule can automatically generate the configuration conversion from 'on' to 'off' from the ground state to the excited state; then calculating the luminescence property of the photoelectric conversion molecules, simulating the conductivity and the electronic evolution of the photoelectric conversion molecules under two configurations, and comparing the mobility of electrons in the molecules under different configurations to verify that the charge separation can be realized; and finally, calculating the optical properties and excited state properties of the optical switch with the 'off' configuration and the photoelectric conversion molecules, and verifying that the photoelectric conversion molecules can return to the 'on' configuration through optical excitation. The method specifically comprises the following steps:
1. electron transfer
(a) Conjugation of photoelectric conversion molecule
According to the known electron donor phenylacetylene (D)nN is the number of phenylacetylene), A photoswitch (S) and an electron acceptor terpyridyl platinum complex (A) are configured, A D-S-A photoelectric conversion molecular model is built, and structure optimization is carried out. With the monomer phenylacetylene (D)1) Azobenzene (azo) and tri-tert-butylpyridoplatinum complex (A)tBu3) For example, the molecular structural formula is shown in formula a below, in this example, relatively stable trans-azo is selected as an initial configuration, the optimal configuration of the molecule obtained after optimization is shown in fig. 1, except for tert-butyl, the rest parts of the molecule are all in the same plane, and the conjugation is very good.
Figure BDA0001542695140000131
(b) Light absorption Properties
Calculating the light absorption property based on the optimal configuration of the molecule, and obtaining trans-azo and D1-AtBu3And D1-azo-AtBu3、Dn-azo-AtBu3(n-3, 5,7) as an example, the absorption spectra are shown in fig. 2 and 3, and fig. 2 shows trans-azo and D provided in the example of the present invention1-AtBu3And D1-azo-AtBu3Molecular UV-VIS absorption Spectrum, FIG. 3 is D provided in an embodiment of the present inventionn-azo-AtBu3(n-3, 5,7) ultraviolet-visible absorption spectrum of the molecule.
As can be seen from fig. 2, the trans azo molecule absorbs uv light; pure D-A System D1-AtBu3Absorb mainly ultraviolet light in the visible rangeAlthough the absorption is in the enclosure, the absorption intensity is weak. When azo molecules are inserted into D1-AtBu3After the molecule is in the middle, a larger conjugated system is formed, so that the absorption peak in the visible light range is red-shifted, and the absorption intensity is greatly enhanced.
As can be seen from fig. 3, when the number of phenylacetylene groups increased, the conjugated system further increased and the absorption strength further increased. Therefore, the photoelectric conversion molecules have good absorption capacity in the visible light range of solar energy, can effectively capture solar energy and generate photo-generated electrons.
(c) Electron transfer
The absorption of light by a molecule is followed by a transition from the ground state to an excited state, where the transition from the ground state to the lowest excited state is the most dominant transition, while electrons will transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital. With Dn-azo-AtBu3(n-1, 3,5,7) as an example, the results are shown in fig. 4-7, and fig. 4 is D provided by an example of the present invention1-azo-AtBu3The molecular orbital wave function corresponding to the transition from the ground state to the excited state of the molecule, and FIG. 5 is D provided in the example of the present invention3-azo-AtBu3FIG. 6 shows the molecular orbital wave function corresponding to the transition from the ground state to the excited state of a molecule, and D is a value obtained by the following example5-azo-AtBu3FIG. 7 shows the molecular orbital wave function corresponding to the transition from the ground state to the excited state of a molecule, and D is a value obtained by the following example7-azo-AtBu3And (3) a molecular orbital wave function corresponding to the transition of the molecule from the ground state to the excited state.
As can be seen from FIGS. 4 to 7, Dn-azo-AtBu3(n ═ 1,3,5,7) molecules transition from the ground state to the first excited state, with the molecular orbital wave function from Dn-azo transition to AtBu3The distribution of the wave function represents the distribution of electrons, which thus pass from D in the processn-azo transfer to AtBu3The above.
The results of the Mulliken charge calculations for the photoelectric conversion molecules also validate this conclusion. With D1-azo-AtBu3For example, from the ground state to a first excited state，AtBu3To which is added 0.79e-, correspondingly, D1A reduction of 0.79 e-from-azo. Description of D1-azo-AtBu3During the transition of the molecule from the ground state to the first excited state, there are 0.79 units of electrons from D1-azo transfer to AtBu3The above.
D1-azo-AtBu3The Mulliken charge analysis of the molecules is shown in table 1.
TABLE 1D1-azo-AtBu3Mulliken charge analysis of molecules
Electronic number (unit e-) Ground state (S0) First excited state (S1) Electronic change (S1-S0)
D1-azo 0.53 -0.26 -0.79
AtBu3 -1.53 -0.74 0.79
As can be seen from fig. 1 to 7 and table 1, the photoelectric conversion molecule of the present invention has a very good planar conjugated structure, and after absorbing visible light, an effective electron transfer occurs, and electrons are transferred from phenylacetylene and the optical switch molecule to the terpyridine platinum complex, that is, from the electron donor and the optical switch molecule to the electron acceptor.
2. On to off configuration transition
(a) Potential energy curve for optical switch configuration conversion
Since the configuration transition of the optical switch molecule occurs in the excited state, the optical switch molecule with lost electrons may also have similar properties to the excited state, in which case the optical switch molecule does not need to be excited by light and may also automatically undergo a configuration transition from "on" to "off", as evidenced by the simulated optical switch configuration transition potential curve. Taking azobenzene (azo), N-hydroxybenzylideneaniline, 1, 2-bis (2, 5-dimethyl-3-thienyl) perfluorocyclopentene, 1, 2-bis (3, 5-dimethyl-2-thienyl) perfluorocyclopentene and dimethyldihydropyrene derivative as examples, the potential energy curves for switching configuration conversion are shown in FIGS. 8-12, FIG. 8 is the configuration conversion potential energy curve of azobenzene (azo) molecule provided in the example of the present invention, FIG. 9 is the configuration conversion potential energy curve of N-hydroxybenzylideneaniline molecule provided in the example of the present invention, FIG. 10 is the configuration conversion potential energy curve of 1, 2-bis (2, 5-dimethyl-3-thienyl) perfluorocyclopentene molecule provided in the example of the present invention, FIG. 11 is 1 provided in the example of the present invention, fig. 12 is a configuration transformation potential energy curve of a molecule of 2-bis (3, 5-dimethyl-2-thienyl) perfluorocyclopentene, which is provided by the present invention.
As can be seen from fig. 8-12, the barrier for the transition of the neutral azobenzene (azo) molecule from the trans to the cis configuration is about 2.5eV, but after the loss of one electron, the barrier is lowered to 0.5 eV. Other optical switch molecules also have similar properties, and after losing one electron, the conformational transition barrier of N-o-hydroxybenzylideneaniline decreases from 6.3kcal/mol to 1.5kcal/mol, the conformational transition barrier of 1, 2-bis (2, 5-dimethyl-3-thienyl) perfluorocyclopentene molecule decreases from 42kcal/mol to 18kcal/mol, the conformational transition barrier of 1, 2-bis (3, 5-dimethyl-2-thienyl) perfluorocyclopentene molecule decreases from 57kcal/mol to 36kcal/mol, and the conformational transition barrier of dimethyldihydropyrene derivative molecule decreases from 41kcal/mol to 25 kcal/mol. The potential energy curve calculation result of the optical switch molecule shows that when the photoelectric conversion molecule absorbs light and generates electron transfer, and the optical switch loses electrons, the configuration conversion barrier of the optical switch molecule is reduced, and the optical switch molecule is more easily converted from an 'on' configuration to an 'off' configuration. The conformational transition of the photoelectric conversion molecule from the ground state to the excited state also confirms this conclusion.
(b) Photoelectric conversion molecular excited state configuration
The photoelectric conversion molecule absorbs light and then undergoes transition from a ground state to an excited state, and since the electron movement speed is fast, the electron transition is completed very quickly, and the rate of change of configuration is relatively slow, the molecule can relax to the configuration of the excited state after the electron transition is completed. With D1-azo-AtBu3Taking the molecule as an example, the configuration of the first excited state is optimized, and the result is shown in FIG. 13, and FIG. 13 is D provided by the embodiment of the invention1-azo-AtBu3Configuration of the first excited state of the molecule.
As can be seen from FIG. 13, D is different from the completely planar conjugated structure of the ground-state optimum configuration1-azo-AtBu3The configuration of the first excited state of the molecule is no longer in the same plane, since the optical switch molecule azo changes automatically from the trans configuration to the cis configuration, i.e., from the "on" configuration to the "off" configuration, disrupting D1-azo-AtBu3Conjugated structure of the molecule.
In summary, the photoelectric conversion molecule of the present invention will cause the configuration conversion barrier of the optical switch molecule to decrease after the transfer of the photo-excited electrons, and the molecule will automatically convert from the "on" configuration to the "off" configuration, so that the planar conjugated structure of the photoelectric conversion molecule is destroyed.
3. Charge separation
After absorption of light by the photoelectric conversion molecules, electrons transition from a ground state to an excited state, and electrons in a higher excited state relax to a first excited state by internal conversion, and then transition from the first excited state back to the ground state, and the transition mode includes radiative transition and non-radiative transition.
(a) Radiation transition
For spokesTransition by jet with D1-azo-AtBu3For the example of a molecule, we calculated the molecular orbital and transition strength of the molecule transitioning from the first excited state back to the ground state as shown in FIG. 14, which is a graph of D provided in FIG. 14 for an example of the present invention1-azo-AtBu3And (3) a molecular orbital wave function corresponding to the molecular first excited state radiation transition.
As can be seen from the figure, D1-azo-AtBu3The molecular orbital distribution of the molecule transitioning from the first excited state back to the ground state is from AtBu3Up transition to D1-azo, i.e. previously from D1-azo transfer to AtBu3Will return to D through the transition1-azo, completing charge recombination; however, the intensity of this radiation transition is only 0.01, i.e. this is a forbidden transition, so AtBu3The electron on (B) cannot return to D by means of radiation transition1-azo。
(b) Radiationless transition
The conductivity of the photoelectric conversion molecule in the "off" configuration is greatly reduced due to the destruction of the conjugated structure. With D1-azo-AtBu3Taking the molecule as an example, the electron tunneling spectrum is calculated, and the result is shown in FIG. 15, and FIG. 15 is D provided by the embodiment of the present invention1-azo-AtBu3Electron tunneling spectra in the molecular "on" and "off" configurations.
As can be seen from FIG. 15, the first electron tunneling peak appears around 1.3eV, i.e., the electrons with energy of 1.3eV at the lowest can pass through D by tunneling1-azo-AtBu3The electron tunneling intensity of the molecule in the 'on' configuration is 98.3 times that of the 'off' configuration, which shows that the conducting capacity of the 'on' configuration is far stronger than that of the D in the 'off' configuration1-azo-AtBu3The transfer of electrons within a molecule, i.e., in the "off" configuration, is difficult to achieve.
Further simulations of the molecular dynamics electron evolution confirm this conclusion. With D1-azo-AtBu3The results are shown in FIG. 16, and FIG. 16 is D provided in the examples of the present invention1-azo-AtBu3Electron evolution profiles in the "on" and "off" configurations of the molecule.
FIG. 16 shows the "on" configuration D1-azo-AtBu3About half of the electrons in the molecule will be from A within 2pstBu3Move to D1-azo, the conclusion of the electron transfer is verified again; and for D in the "off" configuration1-azo-AtBu3Molecule at AtBu3The electrons above hardly flow within 2ps, indicating that the electrons are almost completely confined to AtBu3Above, cannot return to D1Azo, the corresponding positive charge can only stay at D1-azo。
In summary, after the photoelectric conversion molecule of the present invention completes electron transfer, electrons on the acceptor cannot return to the donor and the optical switch by radiative transition or nonradiative transition, excited electrons will be confined on the acceptor, and corresponding positive charges will remain on the donor and the optical switch, thereby achieving efficient charge separation.
4. Off to on configuration transition
When the excited electrons generated on the photoelectric conversion molecules are consumed, the molecules will return to the ground state, but since the excited state of the molecules is in the "off" configuration, the molecules will preferentially return to the ground state of the "off" configuration, and the molecules at this time will have similar properties to those of the "off" configuration photoswitch, i.e., after absorption of light, configuration conversion occurs. In cis azo and "off configuration D1-azo-AtBu3The light absorption properties were calculated for the molecule example, and the results are shown in FIGS. 17 and 18, and FIG. 17 shows cis azo and "off" configuration D provided by the example of the present invention1-azo-AtBu3Molecular UV-VIS absorption Spectrum, FIG. 18 shows cis azo and "off configuration D provided by an example of the present invention1-azo-AtBu3And (3) the molecular orbital wave function corresponding to the transition of the molecule from the ground state to the first excited state.
As can be seen from FIGS. 17 and 18, the maximum wavelength absorption of the cis azo molecule occurs in the visible range, as well as the "off" configuration D1-azo-AtBu3The maximum wavelength absorption of the molecule also occurs in the visible range and the two absorption peaks are comparable in intensity but red-shifted relative to the cis azo wavelength. From the view point of the molecular orbital wave function of the transition from the ground state to the first excited state, the orbital distribution of the cis azo molecule is related to the "off" configuration D1-azo-AtBu3The azo parts in the molecule have basically the same orbital distribution, which shows that the two correspond to the same excited state, i.e. the cis azo molecule is connected to D1-azo-AtBu3The molecule is then unchanged in its first excited state properties. It is known that the cis azo molecule is converted to the trans configuration after being photoexcited to a first excited state, and is therefore in the "off" configuration D1-azo-AtBu3The same transformation occurs in the azo portion of the molecule after it has been excited to the first excited state.
In summary, the photoelectric conversion molecule of the present invention reaches the ground state of the "off" configuration after the excited electrons are consumed, and then absorbs visible light again to return to the "on" configuration, thereby realizing automatic cycle.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (7)

1. An auto-regulating photoelectric conversion molecule characterized by having a structure represented by formula b:
Figure DEST_PATH_IMAGE001
formula b;
wherein n is 1,3,5 or 7.
2. The method for preparing the autoregulated photoelectric conversion molecule according to claim 1, comprising the steps of:
A) reacting the photoswitch molecules with an electron donor compound and acetylene in tetrahydrofuran under the action of a catalyst to obtain photoswitch molecules, wherein one end of each photoswitch molecule is substituted by an electron donor, and the other end of each photoswitch molecule is substituted by acetylene;
B) dissolving the photoswitch molecule obtained in the step A) and an electron acceptor compound in dichloromethane, reacting under the action of a catalyst, purifying a crude product by column chromatography, and recrystallizing to obtain an automatically regulated photoelectric conversion molecule;
the optical switch molecule is 4, 4' -diiodoazobenzene;
the electron donor compound is phenylacetylene;
the electron acceptor compound is 4-phenyl-2, 2 ', 6', 2 '' -platinum terpyridine;
in the step A), the catalyst is bis (triphenylphosphine) palladium dichloride and cuprous iodide;
in the step B), the catalyst is cuprous iodide.
3. The production method according to claim 2, wherein in the step a), the molar ratio of the photoswitch molecule, the electron donor compound, and acetylene is 1:1: 1; the reaction is carried out under the action of N, N-diisophenylethylamine; the reaction is carried out under the protection of nitrogen, the reaction temperature is 50 ℃, and the reaction time is 20-50 h.
4. The process according to claim 2, wherein in step B), the reaction is carried out under the action of diisopropylamine; the reaction is carried out in an inert argon atmosphere, and the reaction time is 17-24 h.
5. The method for preparing the autoregulated photoelectric conversion molecule according to claim 1, comprising the steps of:
a') dissolving photoswitch molecules with one end substituted by an electron donor and the other end substituted by acetylene and potassium hydroxide in anhydrous methanol, and stirring to obtain a mixed solution;
b') adding an electron acceptor compound and cuprous iodide into the mixed solution, stirring for reaction, and purifying to obtain automatically regulated photoelectric conversion molecules;
the optical switch molecule is 4, 4' -diiodoazobenzene;
the electron donor is phenylacetylene;
the electron acceptor compound is 4-phenyl-2, 2 ', 6', 2 '' -platinum terpyridine.
6. The method according to claim 5, wherein the stirring time in step A') is 30 min.
7. The process according to claim 5, wherein in step B'), the stirring reaction is carried out under the condition of keeping out light for 24 h.
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Address before: 230000 96 Jinzhai Road, Hefei City, Anhui Province

Patentee before: Jiang Jun

Patentee before: Luo Yi

Effective date of registration: 20221026

Address after: 230000 96 Jinzhai Road, Hefei City, Anhui Province

Patentee after: Jiang Jun

Patentee after: Luo Yi

Address before: 230026 Jinzhai Road, Baohe District, Hefei, Anhui Province, No. 96

Patentee before: University of Science and Technology of China

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