Fused ring compounds and methods of manufacture and use

Abstract

The present application aims to provide a fused ring compound, a manufacturing method and an application, the fused ring compound has the structural characteristics shown in formula (I), wherein each group is defined as described in the specification. The fused ring compound has a fast excitation state charge separation rate in a high-polarity solution system, a long excitation state charge separation state life in a low-polarity solution system, and can form a system with super-fast charge separation and super-slow charge recombination under the condition of film aggregation. In addition, this property is independent of the way of film aggregation, greatly reducing the requirements and cost of processing technology, and greatly widening the application of the material in the field of photoelectric conversion.

Description

TECHNICAL FIELD

[0001] The present application relates to the preparation and control of excited state of optoelectronic functional materials and application fields, in particular to a control method for obtaining a system with both ultrafast charge separation and ultralow recombination by changing the dispersion or aggregation system of derivatives in situ. BACKGROUND

[0002] Under the background of alleviating energy crisis and realizing sustainable development in today's world, optoelectronic materials are favored because they can make full use of solar energy, a clean and renewable energy. In the process of light energy-electricity / chemical energy conversion, the most critical step is the charge separation of optoelectronic materials under photoexcitation, which plays a crucial role in improving the key performance of energy conversion efficiency.

[0003] Ultrafast charge separation and ultralow charge recombination enable excited state electrons to have more opportunities to play a role in subsequent photophysical processes, which is the key to obtaining high energy conversion efficiency and carrier yield. Among them, the ultrafast process of charge separation generally refers to the charge separation occurring within picoseconds or even sub-picoseconds (femtoseconds), while the ultralow process of charge recombination, i.e. long-lived charge separation state, generally refers to the time (lifetime) of charge recombination being more than 1000 times longer than that of charge separation. The commonly used strategy to obtain ultrafast charge separation system mainly includes increasing the delocalized state of electron wave function to improve the coupling effect and reduce the Coulomb barrier of charge separation, thereby accelerating the charge separation, such as fullerene: polymer blend solar cell materials. However, the polymer donor has the disadvantages of difficulty in determining molecular structure and molecular weight, and the micro-morphology structure and the photoelectric properties determined thereby of the blend are significantly dependent on the processing technology, which makes it difficult for such materials to become a means of regulating the excited state charge separation process in terms of repeatability or mechanism research. The commonly used strategy to obtain long-lived charge separation state mainly includes designing a donor-acceptor structure with energy level gradient, such as donor 1-donor 2-acceptor, or donor-acceptor 2-acceptor 1, reducing the electronic coupling of the two ends of the molecule through the action of the intermediate donor or acceptor bridge, thereby reducing the charge recombination rate and increasing the lifetime of the charge separation state. However, such structure design and preparation is relatively complex, and the multi-step synthesis makes the final yield low, which is also difficult to become a simple and effective means of regulating the excited state charge separation.

[0004] C 60Fullerene is a good electron acceptor due to its high electron affinity and low reorganization energy. In addition, due to the spherical structure of fullerene molecules, three-dimensional electron coupling can be significantly improved in optoelectronic materials, the electron wave function delocalization is increased, the electron transfer is accelerated, the charge separation yield is improved, and fullerene is often used as a functional layer doping material for solar cells, such as PC61BM, PC71BM and the like. The structure with indenothiophene as a core unit has a rigid donor fused ring skeleton and an alkyl side chain with large steric hindrance, which can inhibit the aggregation of the donor part and improve the phase separation degree of the aggregation system. Therefore, the fullerene is selected as the electron acceptor, the indenothiophene derivative is selected as the electron donor, and the covalent derivative is modified. After aggregation, on the one hand, the aggregation degree of the donor can be reduced, and the coupling of the donor can be reduced, and on the other hand, the aggregation of the fullerene part can be improved, and the electron coupling can be improved, so that greater intermolecular electron delocalization can be achieved to obtain ultrafast charge separation and intermolecular charge recombination to obtain a long-life charge separation state. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of a fused ring compound and a charge separation regulation method thereof, wherein the fused ring compound has a fast excitation state charge separation rate in a high-polarity solution system, a long excitation state charge separation state life in a low-polarity solution system, and can form a system with ultrafast charge separation and ultralow charge recombination under the condition of aggregation into a film.

[0006] In one aspect of the present application, a fused ring compound is provided, which has a structure represented by formula (I).

[0007]

[0008] In formula (I),

[0009] Full represents a fullerene material;

[0010] R1 represents an alkyl group;

[0011] Ar1 is selected from the structure represented by formula (II):

[0012]

[0013] In formula (II), R2 is a long-chain alkyl group; Ar3 is nothing or an aryl group or a heteroaryl group;

[0014] Ar2 is nothing or an aryl group or a heteroaryl group;

[0015] X is selected from one of C, N, O and S.

[0016] In some specific embodiments, the fullerene is C2n (n≥10, n≠11);

[0017] Preferably, the fullerene is C 60 C 70 Or metal fullerene;

[0018] Preferably, R1 is selected from C1-C6 alkyl groups;

[0019] Preferably, R1 is selected from methyl, ethyl, or hexyl;

[0020] More preferably, R1 is ethyl;

[0021] Preferably, Ar1 is a long-chain alkyl, aralkyl, or heteroarylalkyl;

[0022] Preferably, Ar2 is absent or aryl, monocyclic heteroaryl, or bicyclic heteroaryl, wherein the aryl or monocyclic heteroaryl group is selected from...

[0023]

[0024] More preferably, Ar2 is

[0025] Preferably, X is selected from O and S, and more preferably, X is S.

[0026] In some specific embodiments, R2 is a long-chain alkyl group with more than 6 carbon atoms; preferably, R2 is selected from -C6H. 13 -C8H 17 -C 10 H 21 More preferably, R2 is -C6H 13 ;

[0027] Preferably, Ar3 is a 5- to 8-membered aryl group or a 5- to 8-membered heteroaryl group; preferably, Ar3 is selected from...

[0028]

[0029] More preferably, Ar3 is

[0030] Preferably, the structure shown in formula (II) has the structure shown in formula (IIa), formula (IIb), formula (IIc) or formula (IId):

[0031]

[0032] In equations (IIa), (IIb), (IIc), or (IId), R2 is defined as described above.

[0033] In some specific embodiments, the compound of formula (I) has the structure shown in formula (Ia), formula (Ib), formula (Ic), or formula (Id):

[0034]

[0035] In some specific embodiments, the fused ring compound has a bulky alkyl side chain to inhibit crystallization under aggregation conditions and to increase the degree of phase separation; the fused ring compound has a rigid fused ring skeleton and an electron-donating group such as thiophene, which can increase the degree of hole delocalization in the excited state and promote charge separation.

[0036] Preferably, the fused ring compound has a structure represented by the following formula (IIIa)-(IIIj):

[0037]

[0038]

[0039] wherein R1 and R2 are defined as above.

[0040] In some specific embodiments, the fused ring compound is selected from the following structures:

[0041]

[0042] wherein,

[0043] Full represents fullerene; R1 is defined as above;

[0044] In some specific embodiments, the fused ring compound is selected from the following compounds:

[0045]

[0046]

[0047] In another aspect of the present application, a preparation method of the above-mentioned fused ring compound is provided, which comprises the following steps: adding fullerene and a fused ring donor compound represented by formula (IV) under certain conditions to obtain a product;

[0048]

[0049] wherein,

[0050] X, Ar1 and Ar2 are defined as above.

[0051] Preferably, the formula (IV) is selected from the following structures:

[0052]

[0053] Preferably, the formula (IV) is selected from the following structures:

[0054] Preferably, the formula (IV) is selected from the following structures:

[0055] R3is selected from -CHO or,

[0056] Preferably, the addition reaction is selected from any one of Diels-Alder reaction, 1,3-dipolar cycloaddition reaction (Prato reaction);

[0057] Preferably, in the fused ring compound of formula (IV), R3is The addition reaction is Diels-Alder reaction, and the preparation method comprises the following steps: adding fullerene and the fused ring compound of formula (IV) to react in the presence of carbon tetrabromide and a base to obtain;

[0058] Preferably, the base is any one of DBU, NaH;

[0059] Preferably, in the preparation method, the molar ratio of the fullerene to the fused ring compound of formula (IV) is 1.1-1.6:1, for example, optionally 1.2-1.5:1, and more preferably 1.2:1.

[0060] Preferably, in the fused ring compound of formula (IV), R3is -CHO; the addition reaction comprises any one of Diels-Alder reaction, 1,3-dipolar cycloaddition reaction, and the preparation method comprises the following steps: adding fullerene and the fused ring compound of formula (IV) to react in the presence of an amino acid to obtain;

[0061] Preferably, the amino acid is selected from any one of N-ethylglycine or N-methylglycine;

[0062] Preferably, in the preparation method, the molar ratio of the fullerene to the fused ring compound of formula (IV) is 1.1-1.8:1, for example, optionally 1.2-1.5:1, and more preferably 1.5:1.

[0063] Preferably, in the preparation method, the molar ratio of the amino acid to the fused ring compound of formula (IV) is 0.7-0.95:1, for example, optionally 0.8-0.9:1, and more preferably 0.9:1.

[0064] In another aspect of the present application, a method for obtaining a fused ring compound with excited state charge ultrafast separation and ultra-slow recombination is provided, which comprises adding fullerene and the fused ring compound of formula (IV) to react in the presence of an amino acid to obtain;

[0065] Preferably, the addition reaction comprises any one of Diels-Alder reaction, 1,3-dipolar cycloaddition reaction;

[0066] Preferably, in the fused ring compound of formula (IV), R3 is CHO; the addition reaction is a 1,3-dipolar cycloaddition reaction, and the preparation method comprises the following steps: adding the fullerene and the compound of formula (IV) in the presence of an amino acid to obtain.

[0067] Another aspect of the present application is to provide a method for regulating the charge separation state of a solution of a fused ring compound, comprising dispersing the above-mentioned fused ring compound or the fused ring compound obtained by the above-mentioned preparation method into a good solvent to prepare a 0.1 mmol / L solution.

[0068] Preferably, the good solvent is toluene, m-xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, trichloromethane, tetrahydrofuran, benzonitrile, etc. with a certain polarity difference.

[0069] Preferably, the selected solvent is low-polarity o-dichlorobenzene (o-DCB) and high-polarity benzonitrile (PhCN).

[0070] Another aspect of the present application is to provide a method for regulating the excited state charge separation of a film system of a fused ring compound independent of the aggregation mode, comprising:

[0071] (1) spin coating film forming method

[0072] Disperse the above-mentioned fused ring compound or the fused ring compound obtained by the above-mentioned preparation method into a certain volume of good solvent to prepare a 5-30 mg / mL solution; use a spin coater, set the rotation speed to 1000-8000 r / min, 30 s / time, and spin coat on a 1 cm×1 cm quartz substrate to prepare a thin film.

[0073] Preferably, the selected good solvent is toluene or trichloromethane.

[0074] Preferably, the selected rotation speed is 3000 r / min or 5000 r / min.

[0075] (2) liquid-liquid interfacial deposition method

[0076] Disperse the above-mentioned fused ring compound or the fused ring compound obtained by the above-mentioned preparation method into a certain volume of good solvent to prepare a near-saturated solution, load into a container, and place a 1 cm×1 cm quartz sheet at the bottom of the container; then slowly add a certain volume of poor solvent to the system, and after standing for a certain period of time, the fused ring compound self-assembles and deposits into a film on the quartz substrate.

[0077] Preferably, the near-saturated solution preparation method is to first prepare a supersaturated solution, filter to remove solid impurities, and then add 1 / 3-1 / 5 volume of the original good solvent.

[0078] Preferably, the selected good solvent includes toluene, m-xylene, mesitylene, dichloromethane, chloroform;

[0079] Preferably, the selected poor solvent includes methanol, isopropanol, n-hexane;

[0080] Preferably, the selected good solvent and poor solvent and the volume ratio thereof include toluene: methanol = 1:2-1:4, mesitylene: methanol = 1:2-1:4, toluene: isopropanol = 1:2-1:5, mesitylene: isopropanol = 1:2-1:5.

[0081] (3) Solvent evaporation method

[0082] The above condensed ring compound or the condensed ring compound obtained by the above preparation method is dispersed in a certain volume of good solvent to prepare a solution with a certain concentration, and then the solution is drop-coated on the surface of a quartz substrate, and after standing and slow evaporation of the solvent, a sample film is grown on the surface of the quartz substrate;

[0083] Preferably, the selected fast-evaporating good solvent includes dichloromethane, chloroform, tetrahydrofuran, toluene;

[0084] Preferably, the selected slow-evaporating good solvent includes chlorobenzene, o-dichlorobenzene, benzonitrile;

[0085] Preferably, the selected solution concentration ranges from 0.1 to 0.01 mmol / mL.

[0086] Another aspect of the present application is to provide a method for testing the excited state charge separation rate and the charge separation state lifetime of a condensed ring compound, comprising:

[0087] (1) using a near-ultraviolet-visible light source to excite the above condensed ring compound or the condensed ring compound prepared by the above method;

[0088] (2) measuring the femtosecond transient absorption spectrum of the above molecule, and combining the spectral evolution to attribute the charge separation state of the excited state evolution;

[0089] (3) global fitting analysis to obtain the kinetic time constant;

[0090] The kinetic time constant includes the kinetic time constant of the charge transfer, charge separation and charge recombination process;

[0091] Preferably, the kinetic time constant of the charge recombination process includes the rate of charge recombination;

[0092] Preferably, the near-ultraviolet-visible light source of step (1) is a light source with an emission wavelength of 266 nm-532 nm;

[0093] Preferably, the near-ultraviolet-visible light source in step (1) is a light source emitting light with a wavelength of 410 nm, which can selectively excite the fused ring donor;

[0094] Preferably, the near-ultraviolet-visible light source in step (1) is a light source emitting light with a wavelength of 350 nm, which can selectively excite the fullerene acceptor.

[0095] In another aspect of the present application, the application provides a use of the above-mentioned fused ring compound or the fused ring compound prepared by the above-mentioned method in the preparation of optoelectronic materials.

[0096] Preferably, it is applied to chemical engineering, material engineering, molecular engineering, energy conversion, transmission and storage.

[0097] Preferably, it is applied to photoelectric conversion, photoluminescence, photocatalytic reaction and simulation of natural photosynthesis.

[0098] Preferably, it is applied to organic solar cells, photocatalytic hydrogen production, photocatalytic reduction of carbon dioxide, photochemical reaction and artificial simulation of photosynthesis.

[0099] Compared with the prior art, the present application has the following advantages:

[0100] (1) The present application is based on a fused ring compound, and discloses a method for regulating the excitation state charge separation process by changing the aggregation state of the molecule.

[0101] (2) The fused ring compound disclosed by the present application can regulate the rate and lifetime of charge separation by solvent polarity. Increasing the polarity can accelerate the charge separation, and decreasing the polarity can prolong the lifetime of the charge separation state.

[0102] (3) The fused ring compound disclosed by the present application can occur in the excitation state charge separation under a simple film aggregation state, and has the characteristics of ultrafast charge separation and superslow charge recombination, that is, it can greatly improve the charge separation rate and significantly increase the lifetime of the charge separation state, overcoming the shortcomings of traditional materials and methods that the charge separation rate is fast and the charge separation state lifetime is long.

[0103] (4) The aggregation of the fused ring compound disclosed by the present application into a film is very simple, and the aggregation into a film by solvent evaporation, interfacial deposition and spin coating can realize ultrafast charge separation and superslow charge recombination, greatly reducing the preparation cost and the dependence on processing technology.

[0104] (5) The fused ring compound described in the application is obtained by an addition reaction, simple synthesis, simple regulation and diversity, good absorption in the visible light region, and the system with ultrafast charge separation and ultra-slow charge recombination can be obtained through aggregation, which solves the problems of complex traditional material design, difficult to obtain two properties, strong dependence on processing technology, etc., and can be used for photocatalytic hydrogen production, photocatalytic reduction of carbon dioxide, solar cell photosensitizer, etc. BRIEF DESCRIPTION OF DRAWINGS

[0105] Figure 1 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0106] Figure 2 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0107] Figure 3 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0108] Figure 4 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0109] Figure 5 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0110] Figure 6 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0111] Figure 7 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0112] Figure 8 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0113] Figure 9 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0114] Figure 10 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0115] Figure 11 Figure 7 is a femtosecond transient absorption spectrum of the film aggregation system of the fused ring compound 1 in Example 7.

[0116] Figure 12 are the excited state species kinetic curves and the respective time constants obtained from global fitting of the fused ring compound 2 in benzonitrile solvent in Example 7. DETAILED DESCRIPTION

[0117] Example 1: Preparation of fused ring compound 1

[0118]

[0119] (1) 0.485 mmol (508.22 mg) of the aldehyde group containing fused ring aniline compound indenodithiophene [3,2-b] dithiophene-2-carboxaldehyde (IDTT-CHO) was dissolved in 250 mL of toluene, and 0.679 mmol (488.66 mg) of C 60 dissolved in 250 mL of toluene, and then 0.443 mmol (i.e. 45.66 mg) of N- ethylglycine was added, and high-purity nitrogen gas was filled as a protective gas, and the cycloaddition reaction was carried out by heating and refluxing at 130°C with stirring, and the reaction was carried out for 6-8 hours; wherein the structure of indenodithiophene [3,2-b] dithiophene-2-carboxaldehyde (IDTT-CHO) is as follows:

[0120]

[0121] (2) After the system was cooled to room temperature, the solution was evaporated to dryness by reduced pressure distillation, and the product was dissolved in a small amount of toluene, and was first separated by silica gel column chromatography, and the separation steps were as follows: the eluent and the proportion of petroleum ether: toluene = 3:1 (volume ratio) were selected, the plate was monitored, and the second fraction was collected; the crude product obtained by separation was evaporated to dryness by reduced pressure distillation, and the residual solid was dissolved in toluene, and the undissolved solid impurities were removed by filtration, and then the product was purified by high performance liquid chromatography, and the purification steps were as follows: Buckyprep column (20 x 250 mm, Cosmosil) was used for separation, toluene was used as the mobile phase, the flow rate of toluene was 6 mL / min, the sample concentration was 1 mg / mL, 6 mL of sample was fixed for each time, the UV monitoring wavelength was 310 nm, the fused ring compound 1 product eluted from the Buckyprep column at a time of 14.8 min, and the product was detected by MALDI-TOF mass spectrometry, and the fused ring compound 1 was obtained.

[0122] 1H NMR (400 MHz, CDC13-d, 298 K) δ 7.47 (s, 2H), δ 7.11-7.17 (m, 8H), δ 7.01-7.08 (m, 8H), δ 6.95 (d, 2H), δ 5.46 (d, 1H), δ 5.14 (s, 1H), δ 4.22 (d, 1H), δ 3.65 (d, 1H), δ 2.52-2.56 (m, 8H), δ 1.43-1.53 (m, 10H), δ 1.18-1.33 (m, 27H), δ 0.84-0.89 (m, 12H); m / z = 1807.

[0123] Example 2: Preparation of fused ring compound 2

[0124]

[0125] (1) 0.13 mmol (150.45 mg) of fused ring aniline compound indenodithiophene [3,2-b] thieno [3,2-b] thien-2-formaldehyde (IBDT-CHO) and 0.194 mmol (150.45 mg) of C 60 dissolved in 120 mL of toluene, and then 0.117 mmol of N-ethyl glycine (i.e. 12.05 mg) was added, and high-purity nitrogen was introduced as a protective gas, and the ring addition reaction was carried out by heating and refluxing at 130°C with stirring, and the reaction was carried out for 6-8 hours; wherein the structure of indenodithiophene [3,2-b] thieno [3,2-b] thien-2-formaldehyde (IBDT-CHO) is as follows:

[0126]

[0127] (2) After the system is cooled to room temperature, the solution is evaporated to dryness by reduced pressure distillation, the product is dissolved in a small amount of toluene, and is first separated by silica gel column chromatography, and the separation steps are: the eluent and the proportion of petroleum ether: toluene = 3:1 (volume ratio) are selected, the plate is monitored, and the second fraction is collected; the crude product obtained by separation is evaporated to dryness by reduced pressure distillation, and the residual solid is dissolved in toluene, and then the undissolved solid impurities are removed by filtration, and then the product is purified by high performance liquid chromatography, and the purification steps are: Buckyprep column (20 x 250 mm, Cosmosil) is used for separation, toluene is used as the mobile phase in the experiment, the flow rate of toluene is 6 mL / min, the sample concentration is 1 mg / mL, 6 mL is fixed for each time, the UV monitoring wavelength is 310 nm, the fused ring compound 1 product has an elution time of 15.3 min on the Buckyprep column, and the product is detected by MALDI-TOF mass spectrometry, and the fused ring compound 1 is obtained.

[0128] 1H NMR (400 MHz, CDCI3-d, 298 K)): δ 7.47 (s, 2H), δ 7.1 1-7.17 (m, 8H), δ 7.01-7.08 (m, 8H), δ 6.95 (d, 2H), δ 5.46 (d, 1 H), δ 5.14 (s, 1 H), δ 4.22 (d, 1 H), δ 3.65 (d, 1 H), δ 2.52-2.56 (m, 8H), δ 1.43-1.53 (m, 10H), δ 1.18-1.33 (m, 27H), δ 0.84-0.89 (m, 12H); m / z = 1920.

[0129] Example 3: Solution dispersion system of fused ring compound

[0130] Two good solvents with significant polarity difference were selected in this example, o-dichlorobenzene with lower polarity and benzonitrile with higher polarity. The fused ring compound donor derivative dissolved well in both solvents. Higher polarity solvent can provide greater driving force for charge separation in the excited state, thus accelerating charge separation and charge recombination. According to Marcus charge transfer theory, the rate of charge separation and recombination increases with increasing polarity, and the time constant, i.e. the lifetime, decreases with increasing polarity.

[0131] A certain mass of fused ring compound 1 was dissolved in o-dichlorobenzene solvent to prepare a solution with a concentration of about 10 -5 -10 -4 mol / L. The absorbance was about 0.5-0.8 OD near the maximum absorption wavelength of 420 nm in a 1 mm optical path cuvette detected by UV-Vis spectrophotometer.

[0132] Similarly, a certain mass of fused ring compound 1 was dissolved in benzonitrile solvent to prepare a solution with a concentration of about 10 -5 -10 - 4 mol / L. The absorbance was about 0.5-0.8 OD near the maximum absorption wavelength of 420 nm in a 1 mm optical path cuvette detected by UV-Vis spectrophotometer.

[0133] A certain mass of fused ring compound 2 was dissolved in o-dichlorobenzene solvent to prepare a solution with a concentration of about 10 -5 -10 -4 mol / L. The absorbance was about 0.5-0.8 OD near the maximum absorption wavelength of 430 nm in a 1 mm optical path cuvette detected by UV-Vis spectrophotometer.

[0134] Similarly, a certain mass of fused ring compound 2 was dissolved in benzonitrile solvent to prepare a solution with a concentration of about 10 -5 -10 - 4The concentration of the solution was 10"5mol / L. The absorbance was about 0.5-0.8 OD at the maximum absorption wavelength of 430 nm.

[0135] Example 4: Preparation of the condensed ring compound film by spin coating method

[0136] 30 mg of the condensed ring compound 1 was dissolved in 1 mL of chloroform, and was fully dissolved by ultrasonic treatment. A spin coater was used, and the rotation speed was set to 1000 r / min, 3000 r / min, 5000 r / min, and 7000 r / min. The rotation time was set to 30 s each time. The film was prepared on a 1 cm x 1 cm quartz plate under nitrogen protection, and 30 microliters of the sample was added each time. The height of the sample was fixed.

[0137] 30 mg of the condensed ring compound 2 was dissolved in 1 mL of chloroform, and was fully dissolved by ultrasonic treatment. A spin coater was used, and the rotation speed was set to 1000 r / min, 3000 r / min, 5000 r / min, and 7000 r / min. The rotation time was set to 30 s each time. The film was prepared on a 1 cm x 1 cm quartz plate under nitrogen protection, and 30 microliters of the sample was added each time. The height of the sample was fixed.

[0138] Example 5: Preparation of the condensed ring compound film by interfacial deposition method

[0139] A certain amount of the condensed ring compound 1 was dissolved in toluene, and was fully dissolved by ultrasonic treatment to prepare a saturated or slightly supersaturated solution. The residual solid impurities were filtered out by using a microporous filter, and 1 / 5 volume of toluene was added to prepare a near-saturated solution. A 1 cm x 1 cm quartz plate was placed at the bottom of a sample bottle, 0.5 mL of the prepared condensed ring compound 1 was added to the sample bottle, and 1.5 mL of methanol was slowly added from the upper part along the wall of the container. The sample was left to stand overnight. The next day, the quartz plate was taken out and dried under vacuum to obtain a self-assembled deposition film. The maximum absorbance was about 0.5-1 OD at the maximum absorption wavelength.

[0140] Similarly, a certain amount of the condensed ring compound 2 was dissolved in toluene, and was fully dissolved by ultrasonic treatment to prepare a saturated or slightly supersaturated solution. The residual solid impurities were filtered out by using a microporous filter, and 1 / 5 volume of toluene was added to prepare a near-saturated solution. A 1 cm x 1 cm quartz plate was placed at the bottom of a sample bottle, 0.5 mL of the prepared condensed ring compound 1 was added to the sample bottle, and 1.5 mL of methanol was slowly added from the upper part along the wall of the container. The sample was left to stand overnight. The next day, the quartz plate was taken out and dried under vacuum to obtain a self-assembled deposition film. The maximum absorbance was about 0.5-1 OD at the maximum absorption wavelength.

[0141] Example 6: Thin film of fused ring compound by solvent evaporation

[0142] A 50 μL aliquot of the o-DCB solution of fused ring compound 1 was dropped onto the surface of a quartz plate and allowed to evaporate. A thin film was left on the surface of the quartz substrate after the solvent evaporated. The maximum absorbance was about 0.3-1 OD at the maximum absorption wavelength by UV-Vis spectrophotometer.

[0143] A 50 μL aliquot of the o-DCB solution of fused ring compound 2 was dropped onto the surface of a quartz plate and allowed to evaporate. A thin film was left on the surface of the quartz substrate after the solvent evaporated. The maximum absorbance was about 0.3-1 OD at the maximum absorption wavelength by UV-Vis spectrophotometer.

[0144] Example 7: Excited state charge separation dynamics of fused ring compounds under different dispersion and aggregation conditions

[0145] The pump light was centered at 410 nm with a pulse power of about 100-500 μW, which was generated by a optical parametric amplifier (TOPAS-800-fs) pumped by a Ti:sapphire regenerative amplifier (centered at 800 nm with a pulse duration of about 25 fs and a pulse energy of about 3 mJ). The seed light was a mode-locked Ti:sapphire laser system (Micra 5, Coherent) and the pump light was generated by a 1 KHz Nd:YLF laser (Evolution 30, Coherent). The weak probe light pulse (less than 0.5 μJ per sample pulse) was generated by a white light continuum (WLC) (rotated at 800 nm in a 4.55 mm thick CaF2 crystal) from 400-700 nm. Both the pump and probe light were linearly polarized. The response of the pump-probe spectrometer was about 80 fs, which was achieved by cross-correlating the pump and probe pulses. The pump and probe light had precise spatial overlap with diameters of 800 μm and 300 μm, respectively, and the center was a 1 mm path length cuvette or a 1 cm x 1 cm quartz plate. The best transient absorption signal was obtained by a laser analyzer (BG-USB-SP620, Ophir-Spiricon).

[0146] The pump and probe pulse delay was varied by changing the optical delay line (minimum 1.56 fs, maximum delay 3.2 ns). The mechanical modulation was used at 500 Hz to manipulate the pump pulse, for example the transient absorption spectrum was recorded with and without the pump pulse. The probe light was first split into two very small parts, one of which was used to monitor the stability of the probe light by two independent photodiode detectors. The other part was split into two, 70% of which was overlapped with the pump light in the sample cell to produce a probe signal, and 30% of which was directed to the sample cell to ensure a good signal to noise ratio.

[0147] The transient pump spectrum absorption map was directly observed by 1024-pixel imaging, and then further processed by ExiPro 2.6 software.

[0148] Detection steps:

[0149] (1) 0.5-2 mL of 10 -5 mol / L-10 -4 mol / L of condensed ring compounds 1 and 2 in o-dichlorobenzene were selected respectively and placed in a 1 mm optical path cuvette with a rotor, and installed on a rotating table with a rotating speed of 2000 rpm to prevent local light damage to the sample;

[0150] (2) The film aggregation sample was a 1 cm x 1 cm quartz sheet, which was directly fixed on the sample table for detection;

[0151] (3) 410 nm visible light was selected to selectively excite the condensed ring donor, and the transient absorption spectrum in the near ultraviolet-visible-near infrared region (wavelength range 350 nm-1600 nm) was detected;

[0152] (4) According to the spectral evolution process of different samples within 5 ns time scale, the local excited state, charge transfer state, charge separation state and other excited state evolution processes were attributed (see Figure 1 、 Figure 3 、 Figure 5 、 Figure 7 、 Figure 9 、 Figure 11 );

[0153] (5) According to the global fitting of the transient absorption spectrum of each derivative, the time constant of each excited state evolution process was attributed, that is, the lifetime of the corresponding excited state, and the reciprocal of which is the rate constant of the process (see Figure 2 、 Figure 4 、 Figure 6 、 Figure 8 、 Figure 10 、 Figure 12 )。

[0154] Since the spectra and dynamics of multiple excited-state species are mixed when a molecule is excited, a global fitting method is used with a continuous model to obtain the main excited-state components and the time constants of the evolution between the corresponding excited-state species, i.e., lifetimes. The criterion for determining charge-separated states is: the presence of excited-state absorption peaks of positive and negative ions (radical ion pairs) on the same time scale; the corresponding time constant is the lifetime of the charge-separated state.

[0155] 7.1: Excited-state evolution, kinetic properties, and lifetime analysis of fused-ring compound 1 in benzonitrile solvent

[0156] Analysis of excited-state evolution process:

[0157] Depend on Figure 1 It can be seen that when the molecule is excited by 410nm pump light, electrons transition to the excited state, and local excited state characteristic absorption first appears near 720nm, then evolves into cation absorption at 580nm, 615nm and 1250nm, reaching the absorption maximum within 20ps; simultaneously with the generation of cations, C at 1050nm... 60 An excited-state absorption signal of anionic radicals is generated, indicating the charge separation process; the duration of radical ion pairs is less than 100 ps.

[0158] Excited-state lifetime analysis:

[0159] Depend on Figure 2 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state goes through a local excited state, a charge transfer state, and a charge separation state, with corresponding time constants of 0.5 ps, 10.8 ps, and 61.9 ps, respectively. Therefore, the time constant of the charge separation process of fused-ring compound 1 in benzonitrile solvent is 10.8 ps, and the lifetime of the charge separation state is 61.9 ps.

[0160] 7.2: Excited-state evolution, kinetic properties, and lifetime analysis of fused-ring compound 1 in o-dichlorobenzene solvent

[0161] Analysis of excited-state evolution process:

[0162] Depend on Figure 3 It can be seen that when the molecule is excited by 410nm pump light, electrons transition to the excited state, and local excited state characteristic absorption first appears near 720nm, then evolves into cation absorption at 580nm, 615nm and 1250nm, reaching the absorption maximum within 100ps; simultaneously with the generation of cations, C at 1050nm... 60 The absorption signal of the excited state of the anion free radical is generated, indicating that the charge separation process has occurred.

[0163] Excited-state lifetime analysis:

[0164] Depend on Figure 4 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state goes through a local excited state, a charge transfer state, and a charge separation state, with corresponding time constants of 0.43 ps, 46.1 ps, and 311.7 ps, respectively. Therefore, the time constant for the charge separation process of fused-ring compound 1 in o-dichlorobenzene solvent is 46.1 ps, and the lifetime of the charge separation state is 311.7 ps. This indicates that the less polar o-dichlorobenzene can regulate charge recombination, extending the lifetime of the charge separation state to five times that in benzonitrile.

[0165] 7.3: Excited-state evolution, kinetic properties detection, and lifetime analysis of the film aggregation system of fused-ring compound 1

[0166] Analysis of excited-state evolution process:

[0167] Depend on Figure 5 It can be seen that when a molecule is excited by 410 nm pump light, electrons transition to an excited state, reaching the absorption maximum within 1 ps; then it relaxes rapidly, charge separation occurs, and C appears at 1050 nm. 60 The excited-state absorption signals of the anion radicals show excited-state absorption signals of the fused-ring donor cation radicals at 580 nm, 615 nm, and 1250 nm; however, these signals do not decay completely within a 5 ns time window.

[0168] Excited-state lifetime analysis:

[0169] Depend on Figure 6 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state can be obtained through charge transfer states and three charge separation states with different vibrational energy levels. The four time constants obtained are: charge transfer to charge separation 0.5 ps, charge separation state relaxation 5.5 ps, charge separation state relaxation 224 ps, and charge recombination 5789 ps. This was later confirmed by nanosecond transient absorption, with the charge recombination time constant being approximately 50 μs. Therefore, the charge separation process time constant in the membrane aggregation system of fused ring compound 1 is 0.5 ps, and the lifetime of the charge separation state is 50 μs, exhibiting characteristics of ultrafast charge separation and ultraslow charge recombination. It is evident that membrane aggregation regulation has a more significant regulatory effect compared to solvent polarity regulation.

[0170] 7.4: Excited-state evolution, kinetic properties, and lifetime analysis of fused-ring compound 2 in benzonitrile solvent

[0171] Analysis of excited-state evolution process:

[0172] Depend onFigure 7 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition to the excited state, and local excited state characteristic absorption first appears near 700 nm to 900 nm, which then evolves into cation absorption at 610 nm, 680 nm, 1250 nm and 1450 nm, reaching the absorption maximum within 20 ps; simultaneously with the generation of cations, C at 1050 nm... 60 The absorption signal of the excited state of the anion free radical is generated, indicating that the charge separation process has occurred.

[0173] Excited-state lifetime analysis:

[0174] Depend on Figure 8 It can be seen that when the molecule is excited by 410nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state goes through a local excited state, a charge transfer state, and a charge separation state, with corresponding time constants of 0.3 ps, 8.8 ps, and 22.4 ps, respectively. Therefore, the time constant of the charge separation process of the fused-ring compound 2 in benzonitrile solvent is 8.8 ps, and the lifetime of the charge separation state is 22.4 ps.

[0175] 7.5: Excited-state evolution, kinetic properties, and lifetime analysis of fused-ring compound 2 in o-dichlorobenzene solvent

[0176] Analysis of excited-state evolution process:

[0177] Depend on Figure 9 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition to the excited state, and local excited state characteristic absorption first appears near 700 nm to 900 nm, which then evolves into cation absorption at 610 nm, 680 nm, 1250 nm and 1450 nm, reaching the absorption maximum within 100 ps; simultaneously with the generation of cations, C at 1050 nm... 60 The absorption signal of the excited state of the anion free radical is generated, indicating that the charge separation process has occurred.

[0178] Excited-state lifetime analysis:

[0179] Depend on Figure 10 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state can be obtained through local excited state, charge transfer state, and charge separation state, with corresponding time constants of 0.3 ps, 24.6 ps, and 122 ps, respectively. Therefore, the time constant of the charge separation process of fused ring compound 2 in o-dichlorobenzene solvent is 24.6 ps, and the lifetime of the charge separation state is 122 ps. This indicates that the less polar o-dichlorobenzene can regulate charge recombination, extending the lifetime of the charge separation state to 5 times that in benzonitrile.

[0180] 7.6: Excited-state evolution, kinetic properties, and lifetime analysis of fused-ring compound 2 in membrane aggregation systems

[0181] Analysis of excited-state evolution process:

[0182] Depend on Figure 11 It can be seen that when a molecule is excited by 410 nm pump light, electrons transition to an excited state, reaching the absorption maximum within 1 ps; then it relaxes rapidly, charge separation occurs, and C appears at 1050 nm. 60 The excited-state absorption signals of anion radicals show excited-state absorption signals of fused-ring donor cation radicals at 610 nm, 680 nm, 1250 nm, and 1450 nm; these signals do not decay completely within a 5 ns time window.

[0183] Excited-state lifetime analysis:

[0184] Depend on Figure 12 It can be seen that when the molecule is excited by 410 nm pump light, electrons transition from the ground state to the excited state. Through global fitting analysis and using a continuous model, the evolution of the excited state can be obtained through charge transfer states and three charge separation states with different vibrational energy levels. The four time constants obtained are: charge transfer to charge separation 0.7 ps, charge separation state relaxation 77 ps, charge separation state relaxation 565 ps, and charge recombination 7903 ps. This was later confirmed by nanosecond transient absorption, and the charge recombination time constant is about 30 μs. Therefore, the charge separation process time constant in the membrane aggregation system of fused ring compound 2 is 0.7 ps, and the lifetime of the charge separation state is 30 μs, which means it has the characteristics of ultrafast charge separation and ultraslow charge recombination. It can be seen that compared with solvent polarity regulation, membrane aggregation regulation has a more significant effect on the regulation of the charge separation state.

[0185] Table 1 summarizes the time constants and charge-separated state lifetimes of excited-state charge separation processes for fused-ring compounds 1 and 2.

[0186] Table 1: Charge separation time constant and charge separation state lifetime

[0187]

[0188] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A fused ring compound having the structure shown in formula (I) : wherein, R 1 is selected from C 1-C 6 alkyl; Ar 1 is a structure shown in formula (IIa) : wherein, X is S. In formula (I), Full denotes a fullerene material, the fullerene being C 60 ; R 1 is selected from C 1-C 6 alkyl; Ar 1 is a structure shown in formula (IIa) : R2is selected from -C6H 13 , -C8H 17 , or -C 10 H 21 ; Ar2is absent or selected from the group consisting of X is S.

2. The fused ring compound according to claim 1, wherein, The fused ring compound has the structure shown in formula (IIIa)-(IIIb) : wherein, Full, R 1, R 2 are each defined as defined in claim 1.

3. The fused ring compound according to claim 2, wherein, The fused ring compound is selected from the following formula: wherein, Full, R 1 are each defined as defined in claim 1.

4. The fused ring compound according to claim 3, wherein, The fused ring compound is selected from the following compounds:

5. A process for the preparation of the fused ring compound of any one of claims 1-4 comprising the steps of: The fullerene is added to a fused ring donor compound shown in formula (IV) under certain conditions to obtain a product; In formula (IV), X, Ar 1, Ar 2 are each defined as defined in any one of claims 1-4. R 3 is -CHO. The addition reaction is a 1, 3-dipolar cycloaddition reaction.

6. The production method according to claim 5, wherein The formula (IV) is selected from the following structures: R 3 is -CHO.

7. The production method according to claim 6, wherein The preparation method comprises the following steps: adding a fullerene to a fused ring donor compound shown in formula (IV) in the presence of an amino acid to obtain a product.

8. The production method according to claim 7, wherein The amino acid is selected from any one of N-ethyl glycine or N-methyl glycine.

9. The production method according to claim 8, wherein In the preparation method, the molar ratio of the fullerene to the fused ring compound shown in formula (IV) is 1.1-1.8:

1.

10. The production method according to claim 9, wherein In the preparation method, the molar ratio of the amino acid to the fused ring compound shown in formula (IV) is 0.7-0.95:

1. 11.A method for regulating the charge separation state of a solution of a fused ring compound, comprising dispersing the fused ring compound of any one of claims 1-4 or prepared by the method of any one of claims 5-10 into a good solvent to prepare a 0.1 mmol / L solution. 12.The method of claim 11, wherein the good solvent is toluene, m-xylene, chlorobenzene, o-dichlorobenzene, dichloromethane, trichloromethane, tetrahydrofuran, benzonitrile. 13.The method of claim 12, wherein the selected good solvent is o-dichlorobenzene and benzonitrile. 14.A method for regulating the charge separation of a fused ring compound aggregation into a film system, which is: a spin coating film forming method dispersing the fused ring compound of any one of claims 1-4 or prepared by the method of any one of claims 5-10 into a good solvent to prepare a 5-30 mg / mL solution; using a spin coater, setting the rotation speed to 1000-8000 r / min, 30 s / time, and spin coating on a 1 cm×1 cm quartz substrate to prepare a thin film. 15.The method of claim 14, wherein the selected good solvent is toluene or trichloromethane. 16.The method of claim 15, wherein the selected rotation speed is 3000 r / min or 5000 r / min. 17.A method for regulating the charge separation of a fused ring compound aggregation into a film system, which is: a liquid-liquid interface deposition method The fused ring compound of any one of claims 1-4 or prepared by the method of any one of claims 5-10 is dispersed in a volume of good solvent, prepared into a near-saturated solution, loaded into a container, and a 1 cm x 1 cm quartz sheet is placed at the bottom of the container; a volume of poor solvent is slowly added to the system, and after standing for a certain period of time, the fused ring compound self-assembles and deposits into a film on the quartz substrate.

18. The method of claim 17, wherein the near-saturated solution is prepared by first preparing a supersaturated solution, filtering to remove solid impurities, and then adding 1 / 3-1 / 5 of the original volume of good solvent.

19. The method of claim 17, wherein the selected good solvent is toluene, m-xylene, mesitylene, dichloromethane, or trichloromethane.

20. The method of claim 17, wherein the selected poor solvent is methanol, isopropanol, or n-hexane.

21. The method of claim 17, wherein the selected good solvent and poor solvent and their volume ratio are toluene:methanol = 1:2-1:4, mesitylene:methanol = 1:2-1:4, toluene:isopropanol = 1:2-1:5, and mesitylene:isopropanol = 1:2-1:

5.

22. A method for regulating the charge separation of a fused ring compound aggregation film system, comprising: solvent evaporation method The fused ring compound of any one of claims 1-4 or prepared by the method of any one of claims 5-10 is dispersed in a volume of good solvent, prepared into a solution of a certain concentration, and the solution is drop-cast onto the surface of a quartz substrate, and after standing and slow evaporation of the solvent, a sample film is grown on the surface of the quartz substrate.

23. The method of claim 22, wherein the selected good solvent is dichloromethane, trichloromethane, tetrahydrofuran, or toluene.

24. The method of claim 22, wherein the selected good solvent is chlorobenzene, o-dichlorobenzene, or benzonitrile.

25. The method of claim 22, wherein the selected solution concentration is in the range of 0.1-0.01 mmol / mL.

26. A method for testing the excited state charge separation rate and charge separation state lifetime of a fused ring compound, comprising: (1) exciting the fused ring compound of any one of claims 1-4 or prepared by the method of any one of claims 5-10 using a near-ultraviolet-visible light source; (2) measuring the femtosecond transient absorption spectrum of the above-mentioned fused ring compound, and attributing the charge separation state of the excited state evolution to the evolution of the spectrum; (3) obtaining the kinetic time constant by global fitting analysis; The kinetic time constant is the kinetic time constant of the charge transfer, charge separation, and charge recombination processes.

27. The method of claim 26, wherein the kinetic time constant of the charge recombination process includes the rate of charge recombination.

28. The method of claim 26, wherein the near-ultraviolet-visible light source of step (1) is a light source with an emission wavelength of 266 nm-532 nm.

29. The test method of claim 26, wherein the near-UV-visible light source in step (1) is a light source emitting light at a wavelength of 410 nm, which can selectively excite fused-ring donors.

30. The test method of claim 26, wherein the near-UV-visible light source in step (1) is a light source emitting light at a wavelength of 350 nm, which can selectively excite fullerene acceptors.

31. Use of the fused-ring compound of any one of claims 1-4 or the fused-ring compound prepared by the method of any one of claims 5-10 in the preparation of optoelectronic materials.

32. The use of claim 31, in the preparation of optoelectronic materials for photoelectric conversion, photoluminescence, photocatalytic reactions, artificial photosynthesis.

33. The use of claim 31, in the preparation of optoelectronic materials for solar cells, photocatalytic hydrogen production, photocatalytic reduction of carbon dioxide, photochemical reactions, artificial photosynthesis.

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