CN101585972B - Photosensitizing dye - Google Patents

Abstract

A photosensitive dye is a ruthenium metal complex represented by formula (1), formula (1)

Description

Photosensitizing dye

technical field

The present invention relates to a solar cell material, and in particular to a photosensitizing dye applicable to dye-sensitized solar cells (DSCs).

Background technique

"Energy" has become one of the important issues that people are actively developing and solving. However, in addition to the depletion of petrochemical energy currently relied on, the excessive use of petrochemical energy has also brought serious pollution problems. Therefore, the development and application of low-pollution renewable energy will become the only way for human beings to seek sustainable development. At present, the sources of renewable energy can be roughly divided into: solar energy, wind power, hydraulic power, tidal power, geothermal energy, and biomass energy. Among the many types of energy, solar energy is the most valued. The reason is that this type of energy is the most abundant and its development and application are not restricted by terrain, landform and other factors. Direct conversion into commonly used electrical energy; its equipment or device is the so-called "solar battery".

In recent years, by And O'Regan proposed a new type of solar cells, the so-called dye-sensitized solar cells (dye-sensitized solar cells; DSCs). In addition to the low manufacturing cost of the solar cell module, the module also has many advantages, such as good photoelectric conversion efficiency, high light transmittance, various colors and flexibility of the module, etc. Therefore, it has attracted close attention from the industry. In general, the structure of a dye-sensitized solar cell includes four parts, which are the cathode/anode electrode that provides the current flow path, the semiconductor material (such as titanium dioxide, zinc oxide, etc.) that accepts and transports electrons, and the self-assembled solar cell. The (self-assembly) form is adsorbed on the dye layer on the surface of the semiconductor material, as well as the electrolyte with the function of transporting holes. The materials used in the various parts of the above-mentioned dye-sensitized solar cell and the joint interface structure between the various parts will affect the photoelectric conversion efficiency of the component. Among them, the dye molecule used in the dye layer is the biggest key to affect the efficiency of the dye-sensitized solar cell.

Therefore, seeking dye molecules with higher light-absorbing ability and using the dye molecules to achieve higher photoelectric conversion efficiency of dye-sensitized solar cells has become one of the very important development directions in the related fields of dye-sensitized solar cells.

Contents of the invention

In view of this, the present invention provides a photosensitive dye, which is suitable as a material for a dye-sensitized solar cell, and the dye-sensitized solar cell using the photosensitive dye has a higher photoelectric conversion efficiency.

The present invention proposes a photosensitizing dye, which is a ruthenium metal complex, which is represented by formula (1)

Formula 1)

Wherein, X ₁ is one of the formulas (2)-(19) and X ₂ represents hydrogen, or X ₂ and X ₁ are both one of the formulas (2)-(19).

R ₁ to R ₄₀ in formulas (3) to (19) are independently H, C _t H _2t+1 (t=1 to 15), OC _v H _2v+1 (v=1 to 15), SC _w H _2w+1 (w=1-15) or one of expressions (36)-(37). Specifically, n in formulas (2)-(19) is 0-2, and m is 1-4. In addition, Y ₁ in formulas (2) to (19) is sulfur (S), methylene group (CH ₂ ), ammonium group (NR) (R is H or C _x H _2x+1 (x=1 to 15 ) one of), oxygen (O) or selenium (Se). It is worth noting that Y ₂ in formulas (2)-(19) can be independently one of formulas (20)-(37).

In addition, Z ₁ in formula (1) is one of formulas (38) to (44), and Z ₂ represents hydrogen or one of formulas (38) to (44). In other words, Z ₂ and Z ₁ may be the same group.

A ₁ in formulas (38)-(44) represents hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)) or any other positively charged ion or group. R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

It should be noted that when X ₂ in formula (1) is hydrogen, Z ₁ and Z ₂ are both formula (38), X ₁ is one of formulas (2) to (5), and formula (2) When n in ~(5) is 0, and Y ₁ is sulfur (S), then Y ₂ in formulas (2) ~ (5) is not formula (20), formula (21) or formula (22) .

In addition to the above, when Z ₁ and Z ₂ in formula (1) are both formula (38) and X ₁ and X ₂ are both formulas (2) to (5), and formula (2) When n in ~(5) is 0 and Y ₁ is sulfur (S), Y ₂ in formulas (2) ~ (5) is not formula (20), formula (21) or formula (22).

In one embodiment of the present invention, the compound structures of the above-mentioned photosensitizing dyes are shown in the following formulas (61)-(67).

R ₆₇ , R ₆₈ , R ₆₉ and R ₇₀ in formula (61) are independently H, _CE H _2E+1 (E=1~6), _OCF H _2F+1 (F=1~6), SC _G H _2G+1 (G=1~15) or one of formulas (36)~(37); R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ in formula (62) are independently H, C _A H _2A+1 (A＝1～15), OC _B H _2B+1 (B＝1～15), SC _D H _2D+1 (D＝1～15) or expression (36)～( 37) One of them; R ₇₅ and R ₇₆ in formula (63) are independently H, C _t H _2t+1 (t=1～15), OC _v H _2v+1 (v=1～15), SC _w H _2w+1 (w=1~15) or one of formulas (36)~(37); R ₇₇ , R ₇₈ , R ₇₉ , R ₈₀ , R ₈₁ and R ₈₂ are independently SC _G H _2G+1 (G=1~15) or one of formulas (36)~(37); R ₈₃ , R ₈₄ , R ₈₅ in formula (67) and R ₈₆ are independently H, C _A H _2A+1 (A=1~15), OC _B H _2B+1 (B=1~15), SC _D H _2D+1 (D=1~15) or It is one of formulas (36)～(37); _A in formulas (61)～(67) independently represents hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)) . In addition, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

In an embodiment of the present invention, the compound structures of the above-mentioned photosensitizing dyes are shown in the following formulas (68)-(74).

A ₁ in formulas (68) to (74) independently represent hydrogen, lithium, sodium, potassium or quaternary ammonium salts (as shown in formula (45)). R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

In one embodiment of the present invention, the compound structures of the above-mentioned photosensitizing dyes are shown in the following formulas (75)-(76).

R ₈₇ , R ₈₈ , R ₈₉ and R ₉₀ in formulas (75)-(76) are independently one of H or C _J H _2J+1 (J=1-15); formulas (75)-(76 ) in A ₁ independently represent hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)). R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

Based on the above, the photosensitizing dye of the present invention has the above-mentioned special groups (namely X ₁ , X ₂ , Z ₁ and Z ₂ ). Therefore, the photosensitizing dye of the present invention has excellent light-absorbing ability. That is to say, the absorption spectrum of the photosensitizing dye of the present invention can be close to the sunlight spectrum, and the photosensitizing dye of the present invention also has a higher absorption coefficient. In other words, when the photosensitizing dye of the present invention is applied to a dye-sensitized solar cell, it can more effectively absorb sunlight and convert it into a current output.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail together with the accompanying drawings.

Description of drawings

Fig. 1 is a graph comparing the absorption spectra of the photosensitizing dyes of the embodiment of the present invention and the known photosensitizing dyes.

Description of main symbols

110, 120, 130, 140, 150: curve

Detailed ways

The present invention proposes a photosensitizing dye, which is a ruthenium metal complex, which is represented by formula (1)

Formula 1)

X ₁ in formula (1) represents one of formulas (2)-(19) and X ₂ represents hydrogen, or X ₂ and X ₁ both represent one of formulas (2)-(19).

R ₁ to R ₄₀ in formulas (2) to (19) are independently H, C _t H _2t+1 (t=1 to 15), OC _v H _2v+1 (v=1 to 15), SC _w H _2w+1 (w=1-15) or one of expressions (36)-(37). Specifically, n is 0-2, and m is 1-4. In addition, Y ₁ in formulas (2) to (19) is sulfur (S), methylene group (CH ₂ ), ammonium group (NR) (R is H or C _x H _2x+1 (x=1 to 15) one of), oxygen (O) or selenium (Se). In addition, Y ₂ in formulas (2)-(19) can be independently one of formulas (20)-(37).

In addition, Z ₁ in formula (1) represents one of formulas (38) to (44), and Z ₂ represents hydrogen, one of formulas (38) to (44). That is, Z ₂ and Z ₁ may be the same group.

A ₁ in formulas (38)-(44) represents hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)) or any other positively charged ion or group. R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

It is worth noting that when X ₂ in formula (1) is hydrogen, Z ₁ and Z ₂ are both formula (38) and X ₁ is one of formula (2)～(5), and formula (2)～ When n in (5) is 0 and _Y1 is sulfur (S), _Y2 therein is not formula (20), formula (21) or formula (22). In addition, when Z ₁ and Z ₂ in formula (1) are both formula (38) and X ₁ and X ₂ are both formulas (2) to (5), and formulas (2) to ( 5) When n is 0 and _Y1 is sulfur (S), _Y2 is not formula (20), formula (21) or formula (22).

In detail, when Z ₁ and Z ₂ in formula (1) are both formula (38) and X ₁ is formula (2) and n in formula (2) is 0, Y ₁ is sulfur (S), and When X ₂ is hydrogen or the same group as X ₁ (formula (2)), the photosensitizing dye of the present invention is shown in formula (46) and formula (47). At this time, _Y2 therein is not formula (20), formula (21), formula (22) or formula (31). In other words, at this time, Y ₂ in formula (2) can only be one of formulas (23)-(30) or formulas (32)-(37).

When Z ₁ and Z ₂ in formula (1) are both formula (38) and X ₁ is formula (3) and n in formula (3) is 0, Y ₁ is sulfur (S), and X ₂ is hydrogen Or when _X1 is the same group (formula (3)), the photosensitizing dye of the present invention is shown in formula (48) and formula (49). At this time, Y ₂ in formula (48) and formula (49) is not formula (20), formula (21), formula (22) or formula (31). In other words, at this time, Y ₂ in formula (48) and formula (49) can only be one of formulas (23)-(30) or formulas (32)-(37).

When _Z1 and _Z2 in formula (1) are both formula (38) and _X1 is formula (4) and n in formula (4) is 0, _Y1 is sulfur (S), _R3 is hydrogen, And when X ₂ is hydrogen or the same group as X ₁ (formula (4)), the photosensitive dye of the present invention is shown in formula (50) and formula (51). Y ₂ in formula (50) and formula (51) is not formula (20), formula (21) or formula (22). In other words, at this time, Y ₂ in formula (50) and formula (51) can only be one of formulas (23)-(37).

When Z ₁ and Z ₂ in formula (1) are both formula (38), X ₁ is formula (5) and n in formula (5) is 0, Y ₁ is sulfur (S), R ₄ ~ R ₇ When both are hydrogen, and X ₂ is hydrogen or the same group as X ₁ (formula (5)), the photosensitizing dye of the present invention is shown in formula (52) and formula (53). At this time, Y ₂ in formula (52) and formula (53) is not formula (20), formula (21) or formula (22). In other words, at this time, Y ₂ in the formula (52) and the formula (53) is one of the formulas (23)-(37).

The photosensitizing dye of the present invention has the above-mentioned special groups (namely X ₁ , X ₂ , Z ₁ and Z ₂ ). Therefore, the photosensitizing dye of the present invention has excellent light-absorbing ability. That is to say, the absorption spectrum of the photosensitizing dye of the present invention can be close to the sunlight spectrum, and has a higher absorption coefficient (absorption coefficient).

Generally speaking, the energy level potential of the excited state of the photosensitizing dye needs to match the energy level potential of the conduction band of the metal oxide used in the dye-sensitized solar cell, such as titanium dioxide or zinc oxide. At this time, electrons can be effectively transferred from the photosensitizing dye to the metal oxide, and the energy loss in the transfer process can be reduced.

In addition, the oxidation potential of the photosensitive dye, the so-called Highest Occupied Molecular Orbital (HOMO) energy level, needs to be slightly lower than the oxidation potential of the electrolyte used, such as iodide ions or other materials with hole transport properties. In this way, the photosensitizing dye that has lost electrons can effectively regain electrons from electrolytes or other materials with hole transport properties to restore them to their original states. Since the photosensitizing dye of the present invention has the above-mentioned special groups (namely X ₁ , X ₂ , Z ₁ and Z ₂ ), its HOMO level is related to the oxidation potential of the cathode and the oxidation potential of the anode used in the dye-sensitized solar cell. The conduction band gaps can match each other. In this way, the dye-sensitized solar cell using the above-mentioned photosensitizing dye can have higher photoelectric conversion efficiency.

In the following examples, the structure of the compound with better light-absorbing ability among the above-mentioned ruthenium complexes will be illustrated.

In one embodiment of the present invention, the compound structure of the photosensitizing dye is shown in the following formulas (61)-(67).

R ₆₇ , R ₆₈ , R ₆₉ and R ₇₀ in formula (61) are independently H, _CE H _2E+1 (E=1~6), _OCF H _2F+1 (F=1~6), SC _G H _2G+1 (G=1~15) or one of formulas (36)~(37); R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ in formula (62) are independently H, C _A H _2A+1 (A＝1～15), OC _B H _2B+1 (B＝1～15), SC _D H _2D+1 (D＝1～15) or expression (36)～( 37) One of them; R ₇₅ and R ₇₆ in formula (63) are independently H, C _t H _2t+1 (t=1～15), OC _v H _2v+1 (v=1～15), SC _w H _2w+1 (w=1~15) or one of formulas (36)~(37); R ₇₇ , R ₇₈ , R ₇₉ , R ₈₀ , R ₈₁ and R ₈₂ are independently SC _G H _2G+1 (G=1~15) or one of formulas (36)~(37); R ₈₃ , R ₈₄ , R ₈₅ in formula (67) and R ₈₆ are independently H, C _A H _2A+1 (A=1~15), OC _B H _2B+1 (B=1~15), SC _D H _2D+1 (D=1~15) or It is one of formulas (36)～(37); _A in formulas (61)～(67) independently represents hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)) . In addition, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

In another embodiment of the present invention, the compound structure of the photosensitizing dye is shown in the following formulas (68)-(74).

A ₁ in formulas (68) to (74) independently represent hydrogen, lithium, sodium, potassium or quaternary ammonium salts (as shown in formula (45)). R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

In other embodiments of the present invention, the compound structure of the photosensitizing dye is shown in the following formulas (75)-(76).

R ₈₇ , R ₈₈ , R ₈₉ and R ₉₀ in formulas (75)-(76) are independently one of H or C _J H _2J+1 (J=1-15); formulas (75)-(76 ) in A ₁ independently represent hydrogen, lithium, sodium, potassium or quaternary ammonium salt (as shown in formula (45)). R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ in formula (45) are each independently H or _Cy H _2y+1 (y=1-15).

Next, the synthesis examples of the three ruthenium metal complexes in the photosensitizing dye of the present invention will be introduced in detail, as well as the analytical data of the experimental results of their light-absorbing ability.

Example 1

This example is a synthetic implementation of a compound of the present invention, which is represented by CYC-B5 below.

CYC-B5 is that _X1 and _X2 in formula (1) are the same group, and _X1 represents the group of the above formula (3), _Y1 of formula (3) is sulfur (S), and n is 0 , m is 2, R ₁ and R ₂ are both hydrogen and Y ₂ is formula (21), and C _i H _2i+1 in formula (21) is C ₈ H ₁₇ . Wherein, Z ₁ and Z ₂ are the same group, and Z ₁ is a group of formula (40), wherein A ₁ represents hydrogen (H).

First, introduce the first ligand of CYC-B5 (expressed as Ligand-1, also can be expressed as 4,4'-bis(5-octyl-2.2'-bithiophen-5-yl)-2,2'-bipyridine ), the synthesis process of the first ligand is as follows.

Wherein, THF represents tetrahydrofuran (tetrahydrofuran, C ₄ H ₈ O), DMF represents dimethylformamide (Dimethylformamide, C ₃ H ₇ NO), and ether represents diethyl ether (C ₄ H ₁₀ O).

First, 4 g of bithiophene was placed in a handy round bottom bottle, and anhydrous tetrahydrofuran solvent was added to dissolve it to obtain a solution. Next, the temperature of the above solution is lowered to -78° C. (for example, liquid nitrogen plus ethanol is used as a refrigerant). Then, 7.6 ml of n-butyl lithium (n-butyl lithium, n-BuLi) solution was added dropwise. The aforementioned n-butyl lithium solution had a concentration of 2.5M and was dissolved in n-hexane. Then, after the temperature of the aforementioned solution returned to room temperature, the stirring was continued for about 15 minutes.

Subsequently, 4.6 ml of bromooctane (1-bromooctane, Br—C ₈ H ₁₇ ) was added to the aforementioned solution, and the aforementioned solution was continuously stirred for about 10 hours. Then, deionized water was added to terminate the reaction, ether was added for extraction, and then the organic layer was collected, and further extracted with saturated aqueous sodium bicarbonate solution, deionized water and saturated aqueous sodium chloride solution respectively. Next, the obtained crude product was purified by column chromatography (eluent was n-hexane), and 5.4 g of an intermediate product was obtained. The intermediate product is represented by formula (54), that is, 2-octyl-2.2'-bithiophene (5-octyl-2.2'-bithiophene, C ₁₆ H ₂₂ S ₂ ), and its yield is 80.5%.

Then, 4.2 g of 2-octylbithiophene was dissolved in anhydrous tetrahydrofuran, and the temperature of the solution was lowered to -78° C. with a refrigerant. Then, 6.0 mL of n-butyllithium (2.5 M, dissolved in n-hexane) was added dropwise. Then, after the temperature of the solution returned to room temperature, the solution was continuously stirred for about two hours.

Next, the temperature of the aforementioned solution was cooled to -78° C. again, and 3.0 g of chlorotrimethyl stannane (C ₃ H ₉ ClSn) (dissolved in an appropriate amount of anhydrous THF) was added.

Subsequently, after the temperature of the reactants in the aforementioned solution returned to room temperature, the solution was continuously stirred for about 12 hours. Then, deionized water was added to terminate the reaction, and further extracted with dichloromethane, deionized water and saturated aqueous sodium chloride solution respectively. Then, collect the organic layer, and then remove the solvent to obtain 6.0 grams of crude product (expressed as formula (55)), the crude product is 8-(trimethyltin)-2-octyl dithiophene (trimethyl( 5-octyl-2.2'-bithiophene) stannane, C ₁₉ H ₃₀ S ₂ Sn).

Next, mix 6.0 grams of 8-(trimethyltin)-2-octylbithiophene with 2.0 grams of 4,4'-bisbromo-2,2'-bipyridine (4,4'-dibromo-2 , 2'-bipyridine) (its synthetic method can refer to I.Murase, Nippon Kagaku Zasshi, 1956,77,682., G.Mnerker and FHCase, J.Am.Chem.Soc., 1958,80,2745. and D .Wenkert and RBWoodward, J.Org.Chem., 1983, 48, 283. and other documents) were dissolved in 60 milliliters of anhydrous dimethylformamide, and 0.44 grams of tetrakis (triphenylphosphine) palladium (Tetrakis (triphenylphosphine) palladium, [Pd(PPh ₃ ) ₄ ]) as catalyst. Then, the reactant was heated to reflux for 22 hours, and after the temperature of the reactant returned to room temperature, 5 wt% ammonium chloride aqueous solution was added to terminate the reaction.

Then, extraction was performed with dichloromethane, and the organic layer was collected. Subsequently, the organic layer was further extracted with saturated sodium bicarbonate, deionized water and saturated sodium chloride respectively, and the solvent of the organic layer was removed to obtain a crude product. Then, the crude product is purified by column chromatography (eluent is n-hexane), and the remaining solid is extracted with a fat extractor (using ethyl acetate as a solvent) to obtain 5.0 grams of The first ligand (denoted as Ligand-1), the yield of the first ligand was 47.0%.

Then, the synthesis route of photosensitizing dye (CYC-B5) containing ruthenium metal complex will be introduced, and the synthesis process of CYC-B5 is as follows.

After preparing the first ligand (denoted as Ligand-1), 0.4323 g of [RuCl ₂ (p-cymene)] ₂ and 1.0 g of the first ligand were dissolved in 50 ml of dehydrated dimethyl formaldehyde amide, and its solution was heated to 80 ° C, after 4 hours of reaction, then added 0.4183 grams of 4,4'-divinyl acid group-2,2'-bipyridine ((4,4'-bis(E-carboxyvinyl )-2,2'-bi-pyridine, dcvbpy) (the synthesis method can refer to literature - C. Klein et al., Inorg. Chem., 2005, 44, 178.), and heated to 160 ° C and reacted for 4 hours. The above chemical reactions need to be carried out in the dark to avoid the production of isomers caused by light.

Next, excess NH ₄ NCS was added, and the temperature was controlled to react at 130° C. for 5 hours. Then, after the reaction was completed, the temperature of the solution was returned to room temperature. Then, the dimethylformamide solvent was removed by a vacuum system, and the obtained solid product was washed with deionized water, an aqueous sodium hydroxide solution with a pH of 12, and diethyl ether, respectively, and then subjected to suction filtration to obtain a crude product.

Then, after dissolving the crude product in methanol and passing it through a column (methanol as eluent), the darker colored fraction was collected and concentrated by spin to remove the methanol solvent. Next, the obtained black solid was firstly treated with ethyl acetate as a solvent to remove impurities soluble in ethyl acetate. Then, the solvent was changed to acetone to remove impurities soluble in acetone. Then, the black solid product washed with ethyl acetate and acetone in sequence is dissolved with a mixed solution of methanol and tetra-butyl ammonium hydroxide (tetra-butyl ammonium hydroxide) aqueous solution, and its liquid is passed through a column ( Sephadex LH-20) and collect the darker part. Then, a few drops of 0.01 M nitric acid aqueous solution were added to adjust the pH value of the liquid containing the product to 3, and then 0.69 g of the product (CYC-B5) was precipitated, with a yield of 40.0%.

The structural analysis and identification of the product (CYC-B5) are as follows:

Theoretical value of mass spectrometry: m/z-1222.2 ([M] ⁺ ); experimental value of mass spectrometry (LRMS(FAB)): m/z-1222.2 (m) ([M] ⁺ ). Mass spectrometry (HRMS(FAB)) found value: m/z-1222.2004. Theoretical value of CYC-B5 (C ₆₀ H ₆₀ N ₆ O ₄ S ₆ Ru) elemental analysis: C, 58.94; H, 4.95; N, 6.87%. Elemental analysis experimental value: C, 58.82; H, 5.79.N, 6.43%. ¹ Hydrogen-nuclear magnetic resonance ( ¹ H-NMR) spectrum signal (500MHz, _H /ppm in d ₆ -DMSO, JHz): 9.26 (H ); 9.15(2protons); 9.05(H); 8.99(H); 8.91(H); 8.22(2protons); 8.15(H) _; (H);7.51(H);7.48(2protons);7.39(2protons);7.34(H);7.25(H);7.21(H);6.98(H);6.90(H);6.84(H);2.81 (2H); 2.78(2H); 1.65(2H); 1.62(2H); 1.26(20H); 0.85(6H).

Example 2

This example is a synthetic implementation of another example of the compound of the present invention, this compound is represented by CYC-B6S below,

In CYC-B6S, X ₁ and X ₂ in the above formula (1) are the same group, and X ₁ is represented by the group of formula (3). Wherein, Y ₁ in formula (3) is sulfur (S), n is 0, m is 1, R ₁ and R ₂ are both hydrogen and Y ₂ is formula (30). Both R ₄₆ and R ₄₇ in formula (30) are C ₄ H ₉ . Wherein, Z ₁ and Z ₂ are the same group, and Z ₁ represents a group of formula (38), and A ₁ represents hydrogen (H).

First, introduce the synthesis route of the first ligand of CYC-B6S (expressed as Ligand-6S), the synthesis process of the first ligand is as follows

Wherein, nitromethane represents nitromethane (CH ₃ NO ₂ ), nitrobenzene represents nitrobenzene (C ₆ H ₅ NO ₂ ), THF represents tetrahydrofuran, DMF represents dimethylformamide, and ether represents ether.

First, put 10 grams of carbazole (C ₁₂ H ₉ N) in a handy round bottom bottle, and add 300 ml of nitromethane (CH ₃ NO ₂ ) and 25 grams of zinc chloride (ZnCl ). Subsequently, 20 ml of tert-butyl chloride (t-BuCl) was added dropwise to the above solution, and the solution was kept stirring at room temperature for 20 hours. Then, the aforementioned solution was transferred to a beaker and 350 ml of water was added to carry out a hydrolysis reaction.

Next, dichloromethane (CH ₂ Cl ₂ ) was added for extraction, and then the organic layer was collected, and further extracted with deionized water and saturated aqueous sodium chloride solution respectively. Then, the obtained crude product is purified by recrystallization (the solvent is n-hexane), and the first intermediate product (expressed as formula (56)) of 10.13 grams can be obtained, 3,6-bis-neobutylcarbazole , and its yield was 60.6%.

Then, the first intermediate product of 10.13 grams (expressed as formula (56)), 6.6g of potassium carbonate (K ₂ CO ₃ ), 6.7g of copper-tin alloy (Cu-bronze) and 7.1g of 2-bromothiophene ( 2-bromo-thiopene, C ₄ H ₃ BrS) was placed in a handy round bottom bottle, and nitrobenzene (nitrobenzene, C ₆ H ₅ NO ₂ ) was added, and the reaction was refluxed for 80 hours under nitrogen gas. Next, remove the solvent, add ammonia water and continue to stir for 2 hours, add a large amount of water and CHCl ₃ for extraction, collect the organic layer, filter the organic layer with magnesium sulfate (Magnesium sulfate, MgSO ₄ ) to remove water, and spin to concentrate to remove most of the of organic solvents. After further purification by column chromatography, the second intermediate product (expressed as formula (57)) can be obtained, and the yield of the second intermediate product is 57.2%.

Next, 1.48 g of the second intermediate product was placed in a round-bottomed flask with a hand, and about 60 ml of anhydrous tetrahydrofuran was added, and the temperature of the round-bottomed flask with a hand was controlled at -78°C (the temperature can be adjusted with ethanol and liquid nitrogen). Then, slowly inject 2.0 ml of n-butyllithium (n-BuLi) solution, which has a concentration of 2.5M and is dissolved in n-hexane. Wait until the temperature naturally returns to room temperature and then stir for another two hours. Then slowly inject 1.1 g of Me ₃ SnCl, wait until the temperature naturally returns to room temperature, and then stir for ten hours. A large amount of water and dichloromethane (Dichloromethane, CH ₂ Cl ₂ ) (soluble in the organic layer) were added for extraction, and the organic layer (lower layer) was collected. The collected organic layer was quickly washed with saturated NaCl _(aq) . The collected product was removed with a rotary concentrator to remove the organic solvent to obtain 2.1 g of the third intermediate product (expressed as formula (58)).

Then, the third intermediate product of 2.1 grams and 2.0 grams of 4,4'-bisbromo-2,2'-bipyridine (its synthetic method can refer to I.Murase, Nippon Kagaku Zasshi, 1956,77,682. , G.Mnerker and FHCase, J.Am.Chem.Soc., 1958, 80, 2745. and D.Wenkert and RB Woodward, J.Org.Chem., 1983, 48, 283. and other documents) dissolved in 60 ml without dimethylformamide in water, and 0.25 g of tetrakis(triphenylphosphine)palladium [Pd(PPh ₃ ) ₄ ] was added as a catalyst. Then, the reactant was heated to reflux for 22 hours, and after the temperature of the reactant returned to room temperature, 5 wt% ammonium chloride aqueous solution was added to terminate the reaction. Then, extraction was performed with dichloromethane, and the organic layer was collected.

Subsequently, the organic layer was further extracted with saturated sodium bicarbonate, deionized water and saturated sodium chloride respectively, and the solvent of the organic layer was removed to obtain a crude product. Then, the crude product is purified by column chromatography (the eluent is n-hexane), and the remaining solid is further purified by a fat extractor (the eluent is ethyl acetate), and finally 1.1 g of the product, Ligand-6S, was obtained with a yield of 71.1%.

Then, the synthesis route of photosensitizing dye (CYC-B6S) containing ruthenium metal complex will be introduced, and the synthesis process of CYC-B6S is as follows.

Here, DMF represents dimethylformamide. After Ligand-6S was prepared, 0.3848 g of [RuCl ₂ (p-cymene)] ₂ and 1.1 g of Ligand-6S were dissolved in 80 ml of dehydrated dimethylformamide, and the solution was heated to 80°C , After reacting for 4 hours, add 0.31 grams of dcbpy ((4,4'-dicarboxylic acid-2,2'-bipyridine);4,4'-dicarboxylicacid-2,2'-bipyridine), and heat to 160 °C, react for 4 hours. Subsequent product purification steps are the same as the previous purification process of CYC-B5. 0.68 g of the product (CYC-B6S) was then obtained in a yield of 40.3%.

Structural analysis identification value of product (CYC-B6S):

Theoretical value of mass spectrometry: m/z-1336.3 ([M] ⁺ ); experimental value of mass spectrometry (LRMS(FAB)): m/z-1336.0 (m) ([M] ⁺ ). Mass spectrometry (HRMS(FAB)) found: m/z-1336.3160. Theoretical value of CYC-B6S (C ₇₂ H ₆₆ N ₈ O ₄ S ₄ Ru) elemental analysis: C, 64.70; H, 4.98; N, 8.38%. Elemental analysis experimental value: C, 64.15; H, 6.10. N, 7.83%. ¹ Hydrogen-nuclear magnetic resonance ( ¹ H-NMR) spectrum signal (500MHz, _H /ppm in d ₆ -DMSO, JHz): 9.45 (H );9.25(H);9.17(H);9.13(H);9.01(H);8.97(H);8.34～8.29(6protons);8.19(H);7.95(H);7.67(2H);7.62 ˜7.57 (4 protons); 7.55 (H); 7.50 (6 protons); 1.43 (18H); 1.39 (18H).

Example 3

This example is the synthesis implementation of the compound of other examples of the present invention, this compound is represented by pre-CYC-B12 below,

Pre-CYC-B12 is that _X1 and _X2 in the formula (1) are the same group, and _X1 represents the group of the above-mentioned formula (10), and n=0, _R20 in the formula (10) is hydrogen atom (H); Y ₁ is sulfur atom (S); and Y ₂ is formula (30), and R ₄₆ and R ₄₇ in formula (30) are both C ₄ H ₉ . Wherein, Z ₁ and Z ₂ are the same group, and Z ₁ is a group of formula (38), wherein A ₁ represents hydrogen (H).

First, the ligands required for the synthesis of pre-CYC-B12 (expressed as Ligand-12, can also be expressed as 4,4'-bis(3,6-di-tert-butyl-carbazol-9-yl-thieno The synthesis route of [3,2-b]thiophen-5-yl)-2,2'-bipyridine) and the synthesis process of ligand (Ligand-12) are shown below.

First, 5.11 grams of the reaction starter (as shown in (59)) was placed in a round-bottomed flask with a hand, and about 65 ml of anhydrous tetrahydrofuran was added, and the temperature of the round-bottomed flask with a hand was controlled at -78°C (ethanol Adjust temperature with liquid nitrogen). Then, slowly inject 5.9 ml of n-butyllithium (n-BuLi) solution, which has a concentration of 2.5M and is dissolved in n-hexane. Wait until the temperature naturally returns to room temperature and then stir for another two hours. Then slowly inject 3.3 g of Me ₃ SnCl, wait until the temperature naturally returns to room temperature, and then stir for ten hours. A large amount of water and chloroform (Chloroform, CHCl ₃ ) (soluble in the organic layer) were added for extraction, and the organic layer (lower layer) was collected. The collected organic layer was quickly washed with saturated NaCl _(aq) . The collected product was removed with a rotary concentrator to remove the organic solvent to obtain 7.0 g of intermediate product (expressed as formula (60)).

Then, 7.0 grams of intermediate product (expressed as formula (60)) and 1.7 grams of 4,4'-bisbromo-2,2'-bipyridine (its synthetic method can refer to I.Murase, Nippon Kagaku Zasshi, 1956, 77, 682., G.Mnerker and FHCase, J.Am.Chem.Soc., 1958, 80, 2745. and D.Wenkert and RB Woodward, J.Org.Chem., 1983, 48, 283. ) was dissolved in 150 ml of anhydrous dimethylformamide, and 0.76 g of tetrakis(triphenylphosphino)palladium [Pd(PPh ₃ ) ₄ ] was added as a catalyst. Then, the reactant was heated to reflux for 22 hours, and after the temperature of the reactant returned to room temperature, 5 wt% ammonium chloride aqueous solution was added to terminate the reaction. Then, extraction was performed with chloroform, and the organic layer was collected. Subsequently, the organic layer was further extracted with saturated sodium bicarbonate, deionized water and saturated sodium chloride respectively, and the solvent of the organic layer was removed to obtain a crude product. Then, the crude product is purified with a fat extractor (solvent is n-hexane), and the remaining solid is further extracted with a fat extractor ((solvent is chloroform)), and finally can be obtained 4.54 grams of product, Ligand-12, yielded 82.7%.

Structural analysis identification value of the product (Ligand-12): mass spectrometry theoretical value: m/z-986.35 ([M] ⁺ ); mass spectrometry (HRMS (FAB)) experimental value: m/z-986.2540 ([M] ⁺ ). ¹ Hydrogen-nuclear magnetic resonance ( ¹ H-NMR) spectrum signal (300MHz, _H /ppmin d-cholorform): 8.77(4H); 8.12(4H); 7.93(2H); 7.60(2H); 7.51(8H); 7.43(2H); 1.47(36H).

Next, the synthesis route of the photosensitizing dye (pre-CYC-B12) containing ruthenium metal complex will be introduced, and the synthesis process of pre-CYC-B12 is as follows.

Here, DMF represents dimethylformamide. After Ligand-12 was prepared, 0.465 g of [RuCl ₂ (p-cymene)] ₂ and 1.5 g of Ligand-6S were dissolved in 125 ml of dehydrated dimethylformamide, and the solution was heated to 80°C , After reacting for 4 hours, add 0.375 grams of dcbpy ((4,4'-dicarboxylic acid-2,2'-bipyridine);4,4'-dicarboxylicacid-2,2'-bipyridine), and heat to 160 °C, react for 4 hours. Subsequent product purification steps are the same as the previous purification process of CYC-B5. 2.30 g of product (pre-CYC-B12) were then obtained in a yield of 53.2%.

Structural analysis identification value of product (pre-CYC-B12):

Mass spectrometry theoretical value: m/z-1448.26 ([M] ⁺ ); mass spectrometry (LRMS(FAB)) experimental value: m/z-1449.6 (m) ([MH] ⁺ ). Mass spectrometry (HRMS(FAB)) found: m/z-1448.2581. CYC- _{B12 ( C76H66N8O4S6Ru ) .} ¹ Hydrogen-nuclear magnetic resonance ( ¹ H-NMR) spectrum signal (500MHz, H/ppm in d ₆ -DMSO): 9.49(H); 9.28(H); 9.23(H); 9.17(H); 9.08(H ); 9.01(H); 8.72(H); 8.53(H); 8.36(H); 8.33(2protons); 8.29(3protons); 8.06(H); 8.00(H); ); 7.56 (4 protons); 7.51 (6 protons); 1.43 (18 protons); 1.40 (18 protons).

Next, the measurement mode of the absorption coefficient of the photosensitizing dye of the present invention is described, and the absorption peak position of the longest wavelength of the absorption coefficient of CYC-B5, CYC-B6S and pre-CYC-B12 and known photosensitizing dyes and the wavelength Absorption coefficient for comparison. The measurement method of the absorption coefficient of the photosensitizing dye of the present invention is to configure the photosensitizing dye solution of known concentration first, then take an appropriate amount of solution and place it in a quartz sample tank, and then put the quartz sample tank into a UV/Vis absorption spectrometer for analysis. Measure, and use Beer's law (Beer'slaw) (A = εbc) to calculate the absorption coefficient. The absorption coefficients of the photosensitizing dyes (CYC-B5, CYC-B6S and pre-CYC-B12) of the present invention were compared with those of known photosensitizing dyes, and the measurement results are shown in Table 1.

J.Photochem.A，2004，164，3.以及M.K.Nazeeruddin et al.，J.Am.Chem.Soc.1993，115，6382.中所提及的“N3“、文献M.K.Nazeeruddin et al.，J.Am.Chem.Soc.，2001，123，1613.所提及的“Black dye”以及文献P.Wang，et al.，Adv.Mater.2004，16，1806.所提及的“Z-910”。It is worth noting that the known photosensitizing dyes listed in Table 1 are respectively literature M.

"N3" mentioned in J.Photochem.A, 2004, 164, 3. and MKNazeeruddin et al., J.Am.Chem.Soc.1993, 115, 6382., document MKNazeeruddin et al., J.Am "Black dye" mentioned in .Chem.Soc., 2001, 123, 1613. and "Z-910" mentioned in P.Wang, et al., Adv.Mater.2004, 16, 1806.

Table 1

Photosensitizing dye Absorption peak wavelength position of longest wavelength (nm) Absorption coefficient of the longest wavelength absorption peak (M ^-1 cm ^-1 ) CYC-B5 562 25100 CYC-B6S 548 16100 Pre-CYC-B12 555 21000 N3 530 14500 black dye 600 7640 Z910 543 16850

It can be seen from Table 1 that the absorption coefficients of CYC-B5, CYC-B6S and pre-CYC-B12 photosensitive dyes of the present invention are higher than those of known dyes and the absorption wavelength is longer than that of known dyes. It can thus be shown that the photosensitizing dye of the present invention has the special groups (X ₁ , X ₂ , Z ₁ , Z ₂ ) shown above, so compared with the light-absorbing ability of known photosensitizing dyes, the photosensitizing dye of the present invention has better The light absorbing ability of the dye is better. Therefore, when the photosensitizing dye of the present invention is applied to a dye-sensitized solar cell, higher photoelectric conversion efficiency can be obtained.

In addition, the absorption spectra of CYC-B5, CYC-B6S, pre-CYC-B12 and N3 obtained by the above measurement method are shown in Fig. 1 . Please refer to Fig. 1, wherein curve 110 represents the absorption spectrum of CYC-B5, curve 120 represents the absorption spectrum of CYC-B6S, and curve 130 represents the absorption spectrum of pre-CYC-B12, and curve 140 represents the absorption spectrum of N3 The spectrum, and the curve 150 represents the sunlight mentioned in the Annual Book of ASTM Standard, G 159-98 Standard tables for references solar spectral radiation at air mass 1.5: direct normal and hemispherical for a 37°tilted surface, Vol.14.04 (2003) Comparing the spectra, it can be found that the curve 110 , the curve 120 and the curve 130 are closer to the curve 150 than the curve 140 . That is to say, the absorption spectrum of CYC-B5, CYC-B6S and pre-CYC-B12 is closer to the sunlight spectrum than that of N3. It can be known that when the photosensitizing dye of the present invention is applied to a dye-sensitized solar cell, higher photoelectric conversion efficiency can be obtained.

Next, the photosensitizing dye of the present invention is used as the material of the dye layer in the dye-sensitized solar cell to manufacture the dye-sensitized solar cell, and measure the component performance thereof.

Using the products CYC-B5, CYC-B6S and pre-CYC-B12 obtained in the above synthesis examples as materials for the dye layer to manufacture dye-sensitized solar cells includes the following steps. Firstly, soak the prepared titanium dioxide (TiO ₂ ) electrode in the solution containing CYC-B5 or CYC-B6S or pre-CYC-B12 for several time. At this time, CYC-B5, CYC-B6S or pre-CYC-B12 will be adsorbed on the surface of the titanium dioxide electrode in a self-assembled manner.

Then, the aforementioned titanium dioxide electrode was taken out, and then the titanium dioxide electrode was slightly rinsed with a solvent and dried, and then the counter electrode was covered and sealed with epoxy resin (epoxy). Then, fill in the electrolyte, and then seal the injection port to complete the preparation of the dye-sensitized solar cell. Dye-sensitized solar cells were manufactured with CYC-B5, CYC-B6S or pre-CYC-B 12 as the material of the dye layer, and the aforementioned two cell components were measured when the light source was AM1.5G (light intensity was 100mW/cm ² ) The measured results of the voltage, current and photoelectric conversion efficiency of the battery module are listed in Table 2 under the simulated sunlight irradiation.

Table 2

Photosensitizing dye Short circuit current density Jsc(mA/cm ² ) Open circuit voltage Voc(mV) Fill factor FF Photoelectric conversion efficiency η (%) CYC-B5 20.1 680 0.638 8.71 CYC-B6S 19.8 777 0.633 9.72 Pre-CYC-B12 14.4 731 0.636 6.72

It can be known from Table 2 that the photoelectric conversion efficiencies of dye-sensitized solar cells made with CYC-B5, CYC-B6S or pre-CYC-B12 as dyes are 8.71%, 9.72% and 6.72%, respectively. Generally speaking, the photoelectric conversion efficiency of dye-sensitized solar cells is between 6% and 10%. That is to say, since the photosensitizing dye of the present invention has the special groups (X ₁ , X ₂ , Z ₁ , Z ₂ ) shown above, the battery components sensitized by the dye of the present invention have good photoelectric conversion efficiency.

In summary, the photosensitizing dye of the present invention has the special groups (X ₁ , X ₂ , Z ₁ , Z ₂ ) shown above, so the absorption spectrum of the photosensitizing dye of the present invention is closer to the sunlight spectrum and Has a high absorption coefficient. Moreover, the HOMO energy level of the photosensitizing dye of the present invention has a good match with the cathode oxidation potential of the general dye-sensitized solar cell and the conduction band energy gap of the anode. Therefore, compared with the known dye-sensitized solar cells, the photoelectric conversion efficiency of the dye-sensitized solar cells of the present invention is higher.

Although the present invention has been disclosed as above with the embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and improvements without departing from the spirit and scope of the present invention. The protection scope of the present invention shall prevail when defined by the appended claims.

Claims (4)

1. A photosensitizing dye is suitable for being applied to a dye-sensitized solar cell, characterized in that, the photosensitizing dye is a ruthenium metal complex, which is represented by formula (1), Formula 1)

Wherein, _X1 is one of the formulas (2)-(19) and _X2 is hydrogen, or _X2 and _X1 are both one of the formulas (2)-(19);

Among them, R ₁ ~ R ₄₀ are independently H, C _t H _2t+1 , OC _v H _2v+1 , SC _w H _2w+1 or one of the expressions (36) ~ (37), t=1 ～15, v=1～15, w=1～15, and n is 0～2, m is 1～4, wherein, Y ₁ is one of sulfur, methenyl, amino, oxygen or selenium, said The amino group is represented by NR, wherein R is one of H or C _x H _2x+1 , x=1~15; Wherein Y in formulas (2)～(19) can be respectively independently one _of formulas (20)～(37);

Wherein, i=1~15 in formula (21), j=1~15 in formula (22), and k=1~15 in formula (23), wherein R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ , R ₄₈ , R ₄₉ , R ₅₀ , R ₅₁ , R 52 , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ and _{R 58 are} independently H, _CA H _{2A +1} , OC _B H _2B+1 , SC _D H _2D+1 or expressions (36)~(37), A=1~15, B=1~15, D=1~15; Wherein R ₄₆ and R ₄₇ are independently H or C _E H _2E+1 , or OC _F H _2F+1 , or SC _G H _2G+1 , E=1~6, F=1~6, G=1~ 15, wherein, R ₅₉ and R ₆₀ in formula (36) and formula (37) are independently H or C _J H _2J+1 , J=1~15, and r is 0~6, and in formula (24), formula (26), formula (27), formula (28) and formula (29) in C _q H _2q q=1～3; wherein _Z1 is one of the formulas (38) to (44), wherein _Z2 represents hydrogen, or one of the formulas (38) to (44), or _Z2 and _Z1 are the same group;

Wherein, R ₆₁ and R ₆₂ are independently one of H, C _I H _2I+1 , OC _J H _2J+1 or SC _K H _2K+1 , I=1~15, J=1~15, K= 1～15; Wherein _A represents hydrogen, lithium, sodium, potassium, a quaternary ammonium salt as shown in formula (45), or any other positively charged ion or group;

Wherein, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ are independently H or C _y H _2y+1 , y=1-15, When Z ₁ and Z ₂ are both formula (38) and X ₁ is formula (2) and n in formula (2) is 0, and Y ₁ is sulfur, and X ₂ is hydrogen or the same group as X ₁ When grouping, Y ₂ in it is not formula (20), formula (21), formula (22) or formula (31), at this time, one of the Y ₂ in formula (2) can only be formula (23)～ (30) or one of formulas (32) to (37); When Z ₁ and Z ₂ are both formula (38) and X ₁ is formula (3) and n in formula (3) is 0, and Y ₁ is sulfur, and X ₂ is hydrogen or the same group as X ₁ When grouping, Y ₂ is not formula (20), formula (21), formula (22) or formula (31), at this time, Y ₂ can only be formula (23)～(30) or formula (32)～( 37) one of them; When Z ₁ and Z ₂ are both formula (38) and X ₁ is formula (4) and n in its formula (4) is 0, and Y ₁ is sulfur, and R ₃ in formula (4) is hydrogen, And when X ₂ is hydrogen or the same group as X ₁ , Y ₂ is not formula (20), formula (21) or formula (22), at this time, Y ₂ is only formula (23)-(37) where one; When Z ₁ and Z ₂ are both formula (38) and X ₁ is formula (5) and n in formula (5) is 0, and Y ₁ is sulfur, and R ₄ to R ₇ in formula (5) Both are hydrogen, and X ₂ is hydrogen or the same group as X ₁ , Y ₂ is not formula (20), formula (21) or formula (22), at this time, Y ₂ is only formula (23)～ (37) ONE OF THEM. 2. The photosensitizing dye according to claim 1, characterized in that, its compound structure is as shown in the following formulas (61) to (67);

Wherein R ₆₇ , R ₆₈ , R ₆₉ and R ₇₀ are independently H or C _E H _2E+1 , or OC _F H _2F+1 , or SC _G H _2G+1 , E=1~6, F=1~ 6, G=1~15; Wherein R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are independently H or C _E H _2E+1 , or OC _F H _2F+1 , or SC _G H _2G+1 , E=1~6, F=1~ 6, G=1~15; Wherein R ₇₅ and R ₇₆ are independently H, C _t H _2t+1 , OC _v H _2v+1 , SC _w H _2w+1 or one of the expressions (36)~(37), t=1~ 15, v=1~15, w=1~15; Wherein R ₇₇ , R ₇₈ , R ₇₉ , R ₈₀ , R ₈₁ and R ₈₂ are independently SC _G H _2G+1 or one of the expressions (36)-(37), G=1-15; Wherein R ₈₃ , R ₈₄ , R ₈₅ and R ₈₆ are independently H or C _E H _2E+1 , or OC _F H _2F+1 , or SC _G H _2G+1 , E=1~6, F=1~ 6, G=1~15; Wherein _A independently represent hydrogen, lithium, sodium, potassium or a quaternary ammonium salt as shown in formula (45); Wherein, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ are independently H or C _y H _2y+1 , y=1-15. 3. The photosensitizing dye according to claim 2, characterized in that, its compound structure is shown in the following formulas (68) to (74);

Wherein _A independently represent hydrogen, lithium, sodium, potassium or a quaternary ammonium salt as shown in formula (45); Wherein, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ are independently H or _Cy H _2y+1 , y=1-15. 4. The photosensitizing dye according to claim 2, characterized in that its compound structure is shown in the following formulas (75) to (76); Wherein R ₈₇ , R ₈₈ , R ₈₉ and R ₉₀ are each independently one of H or C _J H _2J+1 , J=1-15; Wherein _A independently represent hydrogen, lithium, sodium, potassium or a quaternary ammonium salt as shown in formula (45);

Wherein, R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ are independently H or _Cy H _2y+1 , y=1-15.

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