CN1534021A - Large conjugated half cyanine dye, its synthesis and its sensitized nano-crystal semiconductor solar energy battery - Google Patents
Large conjugated half cyanine dye, its synthesis and its sensitized nano-crystal semiconductor solar energy battery Download PDFInfo
- Publication number
- CN1534021A CN1534021A CNA031077145A CN03107714A CN1534021A CN 1534021 A CN1534021 A CN 1534021A CN A031077145 A CNA031077145 A CN A031077145A CN 03107714 A CN03107714 A CN 03107714A CN 1534021 A CN1534021 A CN 1534021A
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- dye
- vinyl
- inner salt
- compound
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- 239000002159 nanocrystal Substances 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title description 37
- 230000015572 biosynthetic process Effects 0.000 title description 36
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- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 18
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 16
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- 125000005647 linker group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/652—Cyanine dyes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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Abstract
A high-conjugated semicyanine dye used as the sensitizer of solar bettery is disclosed. It has the molecular structure: electronic doner-pi conjugated system-electronic doner (D-pi-A) and the formula: D-pi-A-Q-G, and heatores high conjugated level. The nano-crystal semiconductor solar battery sensitized by it has high conversion rate and stability.
Description
Technical Field
The present invention relates to a novel solar cell sensitizer, and more particularly, to a sulfonic acid-or carboxylic acid-containing hemicyanine dye useful as a solar cell sensitizer having a large degree of conjugation as compared with known hemicyanine dye sensitizers, and a sensitized nanocrystalline semiconductor solar cell having excellent effects of high conversion rate and good stability.
Background
With the continuous growth of the world population, humans face two major challenges, food and energy. The development of new clean energy has become an important issue.
According to statistics, the solar radiation reaching the ground every year is 3 multiplied by 1024J (equivalent to 130 ten thousand tons of standard coal), if 1/1000, which is the global surface, is covered with a solar cell with 10% conversion efficiency, the energy demand of all human beings can be satisfied. Therefore, the conversion of solar energy into electrical energy has become one of the important research areas in recent years. At present, a novel thin-film solar cell, particularly a dye-sensitized titanium dioxide nanocrystalline solar cell, which is one of solar cell types, has the advantages of high conversion efficiency, simple preparation process and low price, and has become a competitor of a traditional solid-state cell.
The dye-sensitized solar cell is composed of a working electrode (a dye-sensitized semiconductor nanocrystalline film, wherein the dye is also called a photosensitizer), a counter electrode and an electrolyte. There are two main classes of current sensitizers, namely metal complexes and pure organic dyes.
Compared with the complex, some pure organic dyes have richer photophysical properties, and better photoelectric conversion effect can be obtained by using the pure organic dyes as the sensitizer, so that the research range of the sensitizer is widened. In addition, the pure organic dye is easy to synthesize and cut, and the research on the organic dye-sensitized solar cell can further reduce the costand avoid the consumption of precious metal resources. Therefore, it is very important work to invent pure organic dye sensitizers with high conversion efficiency.
The inventors found that various dye systems simultaneously have excellent second-order nonlinear optical properties and photoelectric conversion properties (see Huangchunhui, Lifuyou, Huangyiyi, "photoelectric functional ultrathin film", chapter five, Beijing university Press, 2001). The molecules have the same characteristics in structure, namely an electron donor group and an electron acceptor group in the molecules are connected through an aromatic electron conjugated system to form an electron donor-pi conjugated system-electron acceptor (D-pi-A) integrated molecular structure. The pi electron conjugated system can be used as an electron transfer channel, so that electron transfer in molecules is easy to occur. In quantum theory, molecules with large second-order nonlinear hyperpolarizability have large dipole moment in the ground state, and they have large dipole moment variation under the action of external field. That is, they are susceptible to intramolecular charge separation under the influence of an external electric field. This is also a requirement for the design of certain photoelectric conversion materials. At present, the D-pi-A structural dyes with better photoelectric conversion effect have two types: neutral dyes and hemicyanine dyes having an internal salt structure.
In terms of neutral dye photosensitizers, Arakawa et al disclose a series of partial cyanine dyes as sensitizers for titanium dioxide nanocrystalline cells, and the compound Mb (18) -N is believed to have highly efficient electron transfer properties. They utilized 13 μm TiO2The nanocrystalline film obtained 9.7mA cm-2The short-circuit photocurrent, open-circuit photovoltage of 0.62V, total energy conversion efficiency was 4.2%, which is the highestvalue in purely organic systems reported in the literature at that time (k.sayama, k.hara, n.mori, m.satsuki, s.suga, s.tsukagoshi, y.abe, h.sugihara, h.arakawa, chem.commu., 2000, 1173).
Mb(18)-N
In 2002, Arakawa et al have also disclosed another series of partial cyanine dyes (Mc [ m, n]]) As a sensitizer of the titanium dioxide nanocrystalline battery, the influence of the length of an alkyl chain and the distance between a binding group and a chromophore skeleton on photoelectric conversion is examined, and the existence of the alkyl chain with proper length is foundThe shorter the distance between the binding group and the chromophore backbone, the better in favour of photocurrent generation. Consider the compound Mc [18, 1]Has high electron transfer performance. They utilized 13 μm TiO2The nanocrystalline film obtained 11.4mA cm-2The short circuit photocurrent of 0.60V, the open circuit photovoltage, the total energy conversion efficiency of 4.5%, andthe stability is quite good (K.Sayama, S.Tsukagaoshi, K.Hara, Y.Ohga, A.Shinpou, Y.Abe, S.Suga, H.Arakawa. J.Phys.Chem.B, 2002, 106(6), 1363).
Mc(m，n)
Another attractive class of photoelectric conversion materials having a D-pi-a structure is the photosensitizers for hemicyanine dyes, whose typical structure is as follows:
the inventors believe that hemicyanine dyes having a D-pi-A structure are used to sensitize TiO2The nanocrystalline electrode should have good sensitizing effect. Based on this idea, the resultsof experiments on titanium dioxide nanocrystalline solar cells sensitized with six compounds (see table below) were reported in 2000 and 2001 successively by royal faith, yufuyou, huangchui, among which some hemicyanine dye-sensitized TiO2The total energy conversion efficiency of the nanocrystalline electrode exceeds 3% (see Z.S.Wang, F.Y.Li, C.H.Huang, L.Wang, M.Wei, L.P.jin, N.Q.Li; J.Phys.chem.B, 2000, 104, 9676-.
PS：R＝CH3；LPS：R＝C16H33QS：R＝CH3；LQS：R＝C16H33
TABLE 1 Performance parameters of six dye-sensitized solar cells
| Isc/mA.cm-2 Voc/mV FF η(％). | |
| PS QS LPS LQS BTS IDS | 7.70 490 0.470 1.87 8.52 401 0.533 1.93 4.87 458 0.519 1.22 3.32 393 0.582 0.80 8.3 490 0.699 3.07 3.5 483 0.721 1.34 |
Wherein, Isc: short circuit photocurrent, VocOpen circuit photovoltage, FF fill factor, η Total energy conversion efficiency
However, none of the above reported pure organic dyes have sufficiently strong sunlight capturing ability, and the maximum absorption peaks of the ultraviolet and visible spectrum are all below 550 nm. To increase the capture of sunlight by the dye, red-shift the maximum absorption of the dye, we must increase the conjugated system of the dye. Based on years of work, the inventor invents a series of large conjugated hemicyanine dyes containing sulfonic acid group and carboxylic acid group and having D-pi-A structure by changing electron donor, conjugated bridge and electron acceptor of the hemicyanine dyes, and sensitizes nanocrystalline TiO with the large conjugated hemicyanine dyes2The electrode, assembled into a solar cell having the structure of fig. 1, achieved excellent effects, thereby completing the present invention.
Brief description of the drawings
FIG. 1 is a diagram of a solar cell device employing a photosensitizing agent of the present invention, wherein:
1-a conductive glass photocathode; 2-semiconductor nanocrystalline film; 3- -a photosensitizing agent; 4-iodine/lithium iodide (I)2/LiI) electrolyte; 5- -plating platinum layer; 6- -conductive glass photoanode;
FIG. 2 is an ultraviolet-visible absorption spectrum of one of the dyes (Dye-7);
FIG. 3 and FIG. 4are respectively a Dye-sensitized TiO of Dye-72The I-V curve and the photocurrent working spectrum of the nanocrystalline solar cell.
Disclosure of Invention
The invention aims to provide novel large conjugated hemicyanine dyes containing acid groups, which have a sensitizing effect on titanium dioxide nanocrystalline electrodes and can be used as light-absorbing sensitizers for preparing dye-sensitized solar cells, and have the following general formula (I).
Another object of the present invention is to provide a method for synthesizing the compound of formula (I).
The invention also provides a titanium dioxide nanocrystalline electrode of a dye-sensitized solar cell prepared by using the compound of the formula (I) as a sensitizer and the dye-sensitized solar cell using the titanium dioxide nanocrystalline electrode.
The hemicyanine dye has a structure that an acid radical group is connected with a D-pi-A chromophore by means of sigma-alkyl chain bridging, and is an inner salt or an onium salt of a nitrogen-containing heterocycle with a structure shown in a formula (I):
D-π-A-Q-G (I)
wherein
The linking group Q is a linear or branched alkylene group having 1 to 20 carbon atoms, preferably a linear or branched alkylene group having 2 to 6 carbon atoms;
the bonding group G being a sulfonate group SO3 -Carboxyl group COOH or carboxyl groupAcid radical group CO2 -；
The group π is an alkenylene group capable of forming a conjugate with the groups D and A, preferably vinylene or 1, 4-butadienyl,more preferably vinylene;
the electron donor group D is one of the following groups:
wherein R isDIs one or more, preferably one or two hydroxyl groups,
RD1is a straight or branched alkyl group having 1 to 20 carbon atoms;
the electron acceptor group a is a large conjugated group of one of the following groups:
wherein
A1-A4 is linked to the Q group at the position of the quaternary nitrogen atom and to the pi group at another bonding position, and
the attachment positions of A1 and A2 to the π group are ortho or para to the position of the attachment Q group,
B1is an N or C atom, and the compound is,
B2is an O, N, S or C atom, and has the following structure,
RAis hydrogen, one or more linear or branched alkyl or alkoxy radicals having 1 to 4 carbon atoms
RA1Is a straight chain alkyl group having 1 to 4 carbon atoms;
with the proviso that when B2When N is, optionally one RA1A group; when B is present2When C is present, it may optionally have one or two RA1A group; when B is present2When O and S are present, no R is presentA1A group.
The term straight-chain or branched alkylene group having 1 to 20 carbon atoms as used herein means a saturated straight-chain or branched alkylene group having 1 to 20 carbon atoms, preferably a straight-chain or branched alkylene group having 2 to 6 carbon atoms, such as ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene and the like.
The term "alkenylene" as used herein refers to an alkenylene group which may form a conjugated system with the groups D and A, and includes vinylene or multiolefins which are themselves conjugated olefinic groups, such as conjugated dienes or conjugated trienes, and the like, e.g., 1, 4-butadienyl, 1, 6-hexanetrienyl, preferably conjugated dienes, more preferably vinylene and 1, 4-butadienyl, most preferably vinylene.
The term "straight-chain or branched alkyl group of 1 to 20 carbon atoms" as used herein means a saturated straight-chain or branched-chain hydrocarbon group having 1 to 20 carbon atoms, preferably a straight-chain or branched alkyl group of 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, decyl, dodecyl, tetradecyl, octadecyl and the like.
The term "straight-chain or branched alkyl group of 1 to 4 carbon atoms" as used herein refers to a saturated straight-chain or branched alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
The term "straight-chain or branched alkoxy group of 1 to 4 carbon atoms" as used herein is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.
The term "straight-chain alkyl group of 1 to 4 carbon atoms" as used herein means a saturated straight-chain hydrocarbon group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl and n-butyl, preferably methyl and ethyl.
In the compounds of the invention, it is preferred that the electron acceptor group A is A4 and the bonding group G is a sulfonate group SO3 -The compound of (1).
In the compounds of the present invention, it is preferred that the electron acceptor group A is A1 and the bonding group G is a carboxylate group CO2 -The compound of (1).
Preferred specific compounds include the compounds Dye-1-Dye-26 given in the examples below, with Dye-5, Dye-10-Dye-25 being more preferred, and Dye-12 being most preferred, i.e., the N- (3-sulfopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]- β -naphthothiazole inner salt.
Another object of the present invention is to provide a method for synthesizing the compound of formula (I). According to the process of the present invention, the compounds of formula (I) may be prepared according to methods known in the art. The starting materials and reagents for preparing the compounds of the invention are known compounds and are commercially available or may be prepared by methods known in the art.
The hemicyanine dyes of the formula (I) according to the invention, in which pi is vinylidene, can be synthesized by the method of the following synthesis scheme I (see Hassner, A.; Birnbaum, D.; Loew, L.M., J.org.chem., 1984, 49, 2546):
scheme I:
wherein A, D, Q and G are as defined above;
the nitrogen heterocyclic compound of the methyl-substituted receptor group A and benzaldehyde derivative are subjected to condensation reaction in acetic anhydride under the heating condition for 24-60 hours to prepare a corresponding large conjugated system, and then the large conjugated system is reacted with substituted carboxylic acid to prepare the required target product.
The bonding group G being a sulfonate group SO3 -The hemicyanine dyes of formula (I) according to the present invention can be prepared according to the following synthesis scheme II:
scheme II:
wherein Q is1Is alkylene having 3 to 4 carbon atoms, A, D and G are as defined above;
the nitrogen-containing heterocyclic compound of the methyl-substituted acceptor group A is reacted with sultone in an organic solvent such as a hydrocarbon solvent, for example, benzene, toluene, xylene or a mixture thereof in the presence of a small amount of piperidine under heating for 24 to 60 hours. The obtained product is reacted with corresponding aldehyde in organic solvent such as alcohol solvent, preferably ethanol, by heating for 8-48 hours, and the desired target product can be obtained.
The bonding group G being a carboxylate group CO2 -The hemicyanine dyes of formula (I) according to the invention can be prepared according to the following synthesis scheme III:
scheme III:
wherein X is a commonly used leaving group, such as halogen; A. d, Q and G are as defined above;
the nitrogen-containing heterocyclic compound of the methyl-substituted acceptor group A is reacted with the substituted carboxylic acid in an organic solvent such as a hydrocarbon solvent, for example, benzene, toluene, xylene or a mixture thereof, in the presence of a small amount of piperidine under heating for 24 to 60 hours. The obtained product is heated and reacted with equimolar aldehyde in an organic solvent such as an alcohol solvent, preferably ethanol for 8 to 48 hours to obtain the desired target product.
The hemicyanine dyes of formula (I) according to the invention, where pi is a butadienyl compound, can be synthesized according to the following synthetic route:
wherein A, D, Q and G are as defined above;
dissolving corresponding heterocyclic onium salt in organic solvent such as anhydrous ethanol, adding equal molar phenylpropenoic aldehyde derivative and small amount of piperidine, refluxing the reaction mixture under stirring for 1-24 hr, cooling to room temperature, removing solvent from the reaction product, and purifying by recrystallization.
The objective product prepared according to each of the above methods can be isolated and purified by a separation and purification method which is conventional in the art, for example, filtration, extraction, drying, distillation, rotary evaporation, recrystallization, column chromatography, etc., and a pure product can be obtained therefrom.
The hemicyanine dye synthesized by the method has good photoelectric conversion function, and the photoelectric conversion performance of the hemicyanine dye reaches or exceeds the level of the currently known similar products.
Therefore, another object of the present invention is to prepare a titanium dioxide nanocrystal electrode of a dye-sensitized solar cell by using the compound of formula (I)as a sensitizer, and to prepare a dye-sensitized solar cell by using the titanium dioxide nanocrystal electrode.
The following are given as specific examples of the compounds of the present invention, which illustrate the invention in detail by way of example, without restricting it in any way.
Examples
The starting materials used in this example are all known compounds, are commercially available, or can be prepared by methods known in the art.
In the following examples, the physicochemical parameters concerned were determined by the following instruments: melting points were measured using a YANACO mp-500 melting point apparatus (thermometer uncorrected);1h NMR was measured using a Bruker Avance model 500 NMR spectrometer; c, H, N element analysis was measured with a VarioEL type element analyzer; IR is measured by a Nicolet Avatar 360 type Fourier infrared spectrometer; UV-Vis was determined by UV-Vis spectroscopy using model GBC Cintra 10 e.
Example 1: n- (3-sulfonatopropyl) -2- [2- (4-N, N-dimethylaminophenyl) ethenyl]Pyridine compoundOnium saltsSynthesis of inner salt (Dye-1)
(1) Preparation of N- (3-sulfopropyl) -2-methylpyridine inner salt
0.93g (0.01mol) of 2-methylpyridine and 1.22g (0.01mol) of 1, 3-propanesultone were dissolved in 20mL of dry benzene under reflux for 48 hours, and then cooled at room temperature. The solid was collected by suction filtration and washed with anhydrous benzene to give 1.46g of a white solid as the inner salt of N- (3-sulfopropyl) -2-methylpyridine. The yield was 68%.
(2) Synthesis of N- (3-sulfopropyl) -2- [2-(4-N, N-dimethylaminophenyl) vinyl]pyridinium inner salt
0.215g (0.001mol) of the product of the above step was dissolved in 30mL of absolute ethanol, and 0.149g (0.001mol) of 4-N, N-dimethylaminobenzaldehyde and one drop of piperidine were added. The reaction mixture was refluxed with stirring for 16 h. And cooling to room temperature. The reaction solution was evaporated to about 10mL, and 30mL of anhydrous ether was added and left in the refrigerator overnight. And (4) carrying out suction filtration, and recrystallizing the obtained solid with ethanol to obtain 0.196g of orange red crystal target compound with the yield of 54%. m.p.>300 ℃.
Elemental analysis C18H22N2O3S: calculated values: c, 62.40; h, 6.40; n, 8.09. measurement: c, 62.12; h, 6.28; and N, 8.13.
1H(500MHz，DMSO)δ：2.11～2.22(m，2H)2.60(t，2H，J＝6.19Hz)3.04(s，6H)4.86(t，2H，J＝7.34 Hz)6.78(d，2H，J＝8.59 Hz)7.50(d，1H，J＝15.68Hz)7.69～7.73(m，1H)7.85(d，2H，J＝8.56Hz)7.97(d，1H，J＝15.55Hz)8.31～8.34(m，1H)8.49(d，1H，J＝8.41Hz)8.76(d，1H，J＝6.00Hz)。
IR(cm-1)：3074，3045，1587，1556，1529，1432，1371，1337，1312，1198，1162，1040，974，942，814，771，609，524。
Example 2: n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) ethenyl]Pyridine compound
Synthesis of inner salt (Dye-2)
Synthesized as described in example 1 except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. After recrystallization from ethanol, 0.285g of the title compound was obtained as orange-red crystals, with a yield of 76%. m.p.258-9 ℃.
Elemental analysis C20H26N2O3S: calculated values: c, 64.14; h, 7.00; n, 7.48. measurement: c, 63.96; h, 6.94; and N, 7.16.
1H(500MHz，DMSO)δ：1.14(t，6H，J＝6.90Hz)2.16(m，2H)2.60(t，2H，J＝6.17Hz)3.45(q，4H，J＝6.90Hz)4.85(t，2H，J＝6.93 z)6.74(d，2H，J＝8.71Hz)7.45(d，1H，J＝15.56Hz)7.69(t，1H，J＝6.61Hz)7.83(d，2H，J＝8.71Hz)7.96(d，1H，J＝15.51Hz)8.30(t，1H，J＝7.88Hz)8.49(d，1H，J＝8.50Hz)8.74(d，1H，J＝6.27Hz)。
IR(cm-1)：2973，1586，1555，1523，1436，1407，1334，1273，1193，1152，1038，814，776，727，526。
Example 3: 1- (3-Sulfonylpropyl) -4- [2- (4-N, N-dimethylaminophenyl) ethenyl]Within pyrimidines
Synthesis of salt (Dye-3)
Synthesized as described in example 1, except that 2-methylpyridine was replaced with 2-methylpyrimidine. After purification by column chromatography (silica gel column, methanol: chloroform: 1: 8), 0.215g of the title compound was obtained as a magenta solid in 62% yield. m.p.281-2 ℃.
Elemental analysis C17H21N3O3S: calculated values: c, 58.77; h, 6.09; n, 12.09. measurement: c, 58.71; h, 6.32; n, 11.96.
1H(500MHz，DMSO)δ：2.19～2.24(m，2H)2.48(t，2H，J＝6.11Hz)3.07(s，6H)4.48(t，2H，J＝6.95Hz)6.82(d，2H，J＝8.87Hz)7.23(d，1H，J＝15.48Hz)7.72(d，2H，J＝8.83Hz)7.91(d，1H，J＝6.81Hz)8.26(d，1H，J＝15.48Hz)8.93(dd，1H，J＝6.84，1.30 Hz)9.37(s，1H)。
IR(cm-1)：3048，2917，1577，1530，1451，1375，1337，1293，1162，1041，942，826，731，524。
Example 4: 1- (3-Sulfonylpropyl) -4- [2- (4-N, N-diethylaminophenyl) ethenyl]Within pyrimidines
Synthesis of salt (Dye-4)
Synthesized as described in example 3, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. After purification by column chromatography (silica gel column, methanol: chloroform: 1: 8), 0.191g of the objective compound was obtained as a magenta solid in 51% yield. m.p.245-6 ℃.
Elemental analysis C19H25N3O3S: calculated values: c, 60.78; h, 6.71; n, 11.19. measurement: c, 60.58; h, 6.85; n, 11.38.
1H(500MHz，DMSO)δ：1.14(t，6H，J＝6.71Hz)2.19～2.25(m，2H)2.52(t，2H，J＝7.54Hz)3.46(q，4H，J＝6.10Hz)4.47(t，2H，J＝6.60Hz)6.78(d，2H，J＝8.47Hz)7.18(d，1H，J＝15.54Hz)7.69(d，2H，J＝8.43Hz)7.89(d，1H，J＝6.56Hz)8.23(d，1H，J＝15.38Hz)8.90(d，1H，J＝6.52Hz)9.34(s，1H)。
IR(cm-1)：3041，2970，1574，1522，1445，1410，1354，1274，1173，1151，1037，815，729，524。
Example 5: 3, 3-dimethyl-N- (3-sulfonatopropyl) -2- [2- (4-N, N-dimethylaminophenyl) ethane
Alkenyl radical]Naphtho [1, 2-d ]]Synthesis of pyrrole inner salt (Dye-5)
Synthesized as described in example 1, except that 2, 3, 3-trimethylnaphtho [1, 2-d]pyrrole was used in place of 2-methylpyridine. The target compound was recrystallized from ethanol to give 0.337g of a dark purple crystal, in 73% yield. m.p.265-6 ℃.
Elemental analysis C27H30N2O3S: calculated values: c, 70.10; h, 6.54; n, 6.06. measurement: c, 70.38; h, 6.55; and N, 6.20.
1H(500MHz，DMSO)δ：2.01(s，6H)2.17～2.19(m，2H)2.69(t，2H，J＝6.50Hz)3.18(s，6H)4.81(t，2H，J＝8.15Hz)6.89(d，2H，J＝9.05Hz)7.55(d，1H，J＝15.70Hz)7.66(d，1H，J＝7.51Hz)7.75(t，1H，J＝7.36Hz)8.08(d，1H，J＝8.91Hz)8.15～8.23(m，4H)8.36(d，1H，J＝8.44Hz)8.45(d，1H，J＝15.66Hz)。
IR(cm-1)：2974，1569，1531，1520，1505，1458，1385，1359，1294，1161，1130，1036，939，821。
Example 6: 3, 3-dimethyl-N- (3-sulfonatopropyl) -2- [2- (4-N, N-diethylaminophenyl) ethyl ester
Alkenyl radical]Naphtho [1, 2-d ]]Synthesis of pyrrole inner salt (Dye-6)
Synthesized as described in example 5, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. The target compound (0.377 g) was obtained as a purplish red crystal by recrystallization from ethanol, with a yield of 77%. m.p.293-4 ℃.
Elemental analysis C29H34N2O3S: calculated values: c, 70.99; h, 6.98; n, 5.71. measurement: c, 71.13; h, 6.94; n, 5.83.
1H(500MHz，DMSO)δ：1.20(t，6H，J＝7.04Hz)2.00(s，6H)2.14～2.20(m，2H)2.69(t，2H，J＝6.31Hz)3.57(q，4H，J＝7.08Hz)4.79(t，2H，J＝7.95Hz)6.88(d，2H，J＝8.99Hz)7.5 1(d，1H，J＝15.69Hz)7.64(t，1H，J＝7.44Hz)7.75(t，1H，J＝7.70Hz)8.06(d，1H，J＝8.87Hz)8.15～8.22(m，4H)8.35(d，1H，J＝8.53Hz)8.42(d，1H，J＝15.64Hz).
IR(cm-1)：2977，2928，1586，1555，1519，1459，1430，1352，1276，1156，1081，1034，944，798，682。
Example 7: 3, 3-dimethyl-N- (3-sulfonatopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxy)
Phenyl) ethenyl]Naphtho [1, 2-d ]]Synthesis of pyrrole inner salt (Dye-7)
Synthesized as described in example 6, except that 2-hydroxy-4-N, N-diethylaminobenzaldehyde was used instead of 4-N, N-dimethylaminobenzaldehyde. Recrystallization from ethanol gave 0.420g of the title compound as greenish black crystals in 83% yield. m.p.>300 ℃.
Elemental analysis C29H34N2O4S: calculated values: c, 68.75; h, 6.76; n, 5.53. measurement: c, 68.50; h, 6.97; and N, 5.63.
1H(500MHz，DMSO)δ：1.19(t，6H，J＝7.83Hz)1.96(s，6H)2.11～2.17(m，2H)2.67(t，2H，J＝6.14Hz)3.51(q，4H，J＝7.81Hz)4.68(d，2H，J＝7.81Hz)6.24(d，1H，J＝1.81Hz)6.51(t，1H，J＝7.94Hz)7.39(d，1H，J＝15.11Hz)7.60(t，1H，J＝7.23Hz)7.72(t，1H，J＝7.62Hz)8.00(d，1H，J＝8.92Hz)8.12～8.19(m，3H)8.36(d，1H，J＝8.34Hz)8.58(d，1H，J＝15.32Hz)10.98(s，1H)。
IR(cm-1)：3442，2972，1585，1572，1528，1505，1415，1359，1303，1269，1177，1153，1069，1035，946，819。
Example 8: n- (3-sulfonatopropyl) -2- [2- (4-N, N-dimethylaminophenyl) ethenyl]Benzo (b) is
Synthesis of oxazolinium salt (Dye-8)
Synthesized as described in example 1, except that 2-methylbenzoxazole was used in place of 2-methylpyridine. The target compound (0.205 g) was recrystallized from ethanol to give bluish violet crystals with a yield of 53%. m.p.>300 ℃.
Elemental analysis C20H22N2O4S: calculated values: c, 62.16; h, 5.74; n, 7.25. measurement: c, 62.26; h, 5.52; and N, 7.12.
1H(500MHz，DMSO)δ：2.19～2.24(m，2H)2.64(t，2H，J＝6.65Hz)3.12(s，6H)4.75(t，2H，J＝7.24Hz)6.86(d，2H，J＝8.75Hz)7.55(d，1H，J＝15.30Hz)7.63～7.69(m，2H)7.92～7.97(m，3H)8.05(d，1H，J＝7.07Hz)8.24(d，1H，J＝15.27Hz)。
IR(cm-1)：2921，1579，1548，1468，1414，1384，1322，1284，1202，1169，1123，1031，932，815，759，717，519。
Example 9: n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) ethenyl]Benzo (b) is
Synthesis of oxazolium inner salt (Dye 9).
Synthesized as described in example 8, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. Recrystallization from ethanol gave 0.253g of the title compound as reddish brown crystals in 61% yield. m.p.262-3 ℃.
Elemental analysis C22H26N2O4S: calculated values: c, 63.75; h, 6.32; n, 6.76. measurement: c, 63.60; h, 6.03; and N, 6.65.
1H(500MHz，DMSO)δ：1.17(t，6H，J＝7.09 Hz)2.19～2.22(m，2H)2.64(t，2H，J＝6.85Hz)3.52(q，4H，J＝7.06Hz)4.74(t，2H，J＝7.32Hz)6.84(d，2H，J＝9.04Hz)7.51(d，1H，J＝15.25Hz)7.62～7.68(m，2H)7.90～7.95(m，3H)8.02～8.05(m，1H)8.22(d，1H，J＝15.22Hz)。
IR(cm-1)：2972，1579，1543，1466，1405，1354，1273，1186，1154，1076，1036，1008，818，750，715，520。
Example 10: n- (3-sulfonatopropyl) -2- [2- (4-N, N-dimethylaminophenyl) ethenyl]- β -naphthalene
Synthesis of benzothiazole inner salt (Dye-10)
Synthesized as described in example 1, except that 2-methyl- β -naphthothiazole was used instead of 2-methylpyridine, and recrystallization from ethanol gave 0.353g of the title compound as bluish purple crystals, in 78% yield, m.p.262-3 ℃.
Elemental analysis C24H24N2O3S2: calculated values: c, 63.69; h, 5.34; n, 6.19. measurement: c, 63.62; h, 4.97; n, 5.92.
1H(500MHz，DMSO)δ：2.46(m，2H)2.88(t，2H，J＝6.11Hz)3.12(s，6H)5.38(t，2H，J＝7.14Hz)6.84(d，2H，J＝8.28Hz)7.83(t，1H，J＝7.23Hz)7.90(t，1H，J＝7.82Hz)8.01～8.11(m，4H)8.23～8.33(m，3H)8.78(d，1H，J＝8.52Hz)。
IR(cm-1)：2912，1573，1528，1458，1378，1324，1274，1167，1034，943，815，730，520。
Example 11: n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) ethenyl]- β -naphthalene
Synthesis of benzothiazole inner salt (Dye-11)
Synthesized as described in example 10, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. The target compound was recrystallized from ethanol to give dark green crystals (0.398 g), with a yield of 83%. m.p.271-2 ℃.
Elemental analysis C26H28N2O3S2: calculated values: c, 64.97; h, 5.89; n, 5.83. measurement: c, 64.61; h, 5.61; and N, 5.61.
1H(500MHz，DMSO)δ：1.17(t，6H，J＝6.60Hz)2.47(m，2H)2.88(t，2H，J＝6.36Hz)3.51(q，4H，J＝6.78Hz)5.36(t，2H，J＝7.56Hz)6.81(d，2H，J＝8.49Hz)7.82(t，1H，J＝7.41Hz)7.89(t，1H，J＝7.33Hz)7.96～8.07(m，4H)8.21～8.31(m，3H)8.77(d，1H，J＝8.59Hz)。
IR(cm-1)：2968，1572，1521，1458，1412，1301，1267，1182，1152，1075，1033，999，817，712。
Example 12: n- (3-sulfopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) ethene
Base of]Synthesis of- β -naphthothiazole inner salt (Dye-12)
The procedure described in example 10 was followed except that 2-hydroxy-4-N, N-diethylaminobenzaldehyde was used instead of 4-N, N-dimethylaminobenzaldehyde. The target compound of a dark purple crystal is obtained by recrystallization with ethanol, wherein the weight is 0.397g, and the yield is 80%. m.p.254-5 ℃.
Elemental analysis C26H28N2O4S2: calculated values: c, 62.88; h, 5.68; n, 5.64. measurement: c, 62.66; h, 5.41; n, 5.57.
δ1H(500MHz，DMSO)δ：1.18(t，6H，J＝7.01Hz)2.44(m，2H)2.86(t，2H，J＝5.80Hz)3.46(q，4H，J＝7.09Hz)5.27(t，2H，J＝8.21Hz)6.21(s，1H)6.44(d，1H，J＝9.27Hz)7.78～7.88(m，3H)8.10(d，1H，J＝9.09Hz)8.17～8.26(m，4H)8.76(d，1H，J＝8.62Hz)10.67(s，1H)。
IR(cm-1)：3440，2971，1570，1520，1456，1419，1257，1206，1155，1111，1033，1000，960，685。
Example 13: n- (4-sulfonatobutyl) -4- [2- (4-N, N-dimethylaminophenyl) ethenyl]Pyridine compound
Synthesis of inner salt (Dye-13)
(1) Preparation of N- (4-sulfobutyl) -4-methylpyridine inner salt
0.93g (0.01mol) of 4-methylpyridine and 1.36g (0.01mol) of 1, 4-butyrolactone were dissolved in 20mL of dry benzene and refluxed for 48 hours, and then cooled at room temperature. The solid was collected by suction filtration and washed with anhydrous benzene to give 1.69g of a white solid as the inner salt of N- (4-sulfobutyl) -4-methylpyridine. The yield was 74%.
(2) Synthesis of N- (4-sulfobutyl) -2- [4- (4-N, N-dimethylaminophenyl) vinyl]pyridine inner salt
0.229g (0.001mol) of the product of the above step was dissolved in 30mL of absolute ethanol, and 0.149g (0.001mol) of 4-N, N-dimethylaminobenzaldehyde and one drop of piperidine were added. The reaction mixture was refluxed with stirring for 16 h. And cooling to room temperature. The reaction solution was evaporated to about 10mL, and 30mL of anhydrous ether was added and left in the refrigerator overnight. Suction filtration is carried out, and the obtained solid is recrystallized by ethanol to obtain 0.219g of a red crystal target compound with the yield of 61 percent. m.p. is more than 300 ℃ (literature value [49]308-9 ℃).
Elemental analysis C19H24N2O3S: calculated values: c, 63.31; h, 6.71; n, 7.77. measurement: c, 63.59; h, 6.42; and N, 7.50.
1H(500MHz，DMSO)δ：1.58～1.61(m，2H)1.94～1.98(m，2H)2.54(t，2H，J＝6.54Hz)2.99(s，6H)4.39(t，2H，J＝6.85Hz)6.76(d，2H，J＝8.45Hz)7.13(d，1H，J＝15.84Hz)7.60(d，2H，J＝8.21Hz)7.85(d，1H，J＝15.99Hz)8.00(d，2H，J＝5.99Hz)8.65(d，2H，J＝6.01Hz)。
IR(cm-1)：2916，1581，1528，1436，1371，1331，1206，1162，1036，946，613，543。
Example 14: n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) ethenyl]Pyridine compound
Synthesis of inner salt (Dye-14)
Synthesized as described in example 13, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. Recrystallization from ethanol gave 0.275g of the title compound as red crystals, 71% yield. m.p. is more than 300 ℃ (document value is 345-6 ℃).
Elemental analysis C21H28N2O3S: calculated values: c, 64.92; h, 7.26; n, 7.21. measurement: c, 64.62; h, 7.22; and N, 7.39.
1H(500MHz，DMSO)δ：1.23(t，6H，J＝7.02Hz)1.83～1.87(m，2H)2.14～2.17(m，2H)2.89(t，2H，J＝7.25Hz)3.50(q，4H，J＝7.04Hz)4.48(t，2H，J＝7.31Hz)6.78(d，2H，J＝8.73Hz)7.07(d，1H，J＝1 5.92Hz)7.61(d，2H，J＝8.71Hz)7.85(d，1H，J＝15.94Hz)7.97(d，2H，J＝6.56Hz)8.59(d，2H，J＝6.56Hz)。
IR(cm-1)：2971，15 81，1523，1474，1405，1361，1329，1271，1169，1151，1036，969，814，523。
Example 15: n- (4-sulfonatobutyl) -4- [2- (4-N, N-dimethylaminophenyl) ethenyl]Quinolines
Synthesis of inner salt (Dye-15)
Synthesized as described in example 13, except that 4-methylquinoline was used in place of 4-methylpyridine. After recrystallization from ethanol, 0.279g of the title compound was obtained as a dark purple crystal, in 68% yield. m.p.>300 ℃.
Elemental analysis C23H26N2O3S: calculated values: c, 67.29; h, 6.38; n, 6.82. measurement: c, 67.57; h, 6.45; n, 6.74.
1H(500MHz，DMSO)δ：1.93～1.99(m，2H)2.22～2.28(m，2H)2.93(t，2H，J＝7.25Hz)3.13(s，6H)4.91(t，2H，J＝6.89Hz)6.87(d，2H，J＝8.69Hz)7.82(d，2H，J＝8.65Hz)7.96～7.99(m，2H)8.11(d，1H，J＝15.51Hz)8.18～8.25(m，2H)8.45(d，1H，J＝8.83Hz)8.88(d，1H，J＝8.52Hz)8.96(d，1H，J＝6.66Hz)。
IR(cm-1)：3090，2922，1579，1556，1527，1437，1373，1326，1231，1191，1166，1033，817，761，600，520。
Example 16: n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) ethenyl]Quinolines
Synthesis of inner salt (Dye-16)
Synthesized as described in example 15, except that 4-N, N-dimethylaminobenzaldehyde was replaced with 4-N, N-diethylaminobenzaldehyde. The target compound was recrystallized from ethanol to give 0.315g of a dark purple crystal with a yield of 72%. m.p.290-1 ℃.
Elemental analysis C25H30N2O3S: calculated values: c, 68.46; h, 6.89; n, 6.39. measurement: c, 68.55; h, 6.71; and N, 6.28.
1H(500MHz，DMSO)δ：1.16(t，6H，J＝6.65Hz)1.68～1.71(m，2H)2.01～2.04(m，2H)2.51(t，2H，J＝7.12Hz)3.48(q，4H，J＝6.68Hz)4.89(t，2H，J＝6.85Hz)6.80(d，2H，J＝8.29Hz)7.85(d，2H，J＝8.33Hz)7.93～7.99(m，2H)8.15～8.20(m，2H)8.33(d，1H，J＝6.33Hz)8.49(d，1H，J＝8.69Hz)9.02(d，1H，J＝8.38Hz)9.14(d，1H，J＝6.31Hz)。
IR(cm-1)：2970，1574，1522，1403，1330，1267，1188，1154，1036，996，762，530。
Example 17: n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylamino-2-hydroxyphenyl) ethene
Base of]Synthesis of quinoline inner salt (Dye-17)
Synthesized as described in example 15, except that 2-hydroxy-4-N, N-diethylaminobenzaldehyde was used instead of 4-N, N-dimethylaminobenzaldehyde. Recrystallization from ethanol gave 0.340g of the title compound as greenish black crystals in 77% yield. m.p.298-9 ℃.
Elemental analysis C25H30N2O4S: calculated values: c, 66.05; h, 6.65; n, 6.16. measurement: c, 66.36; h, 6.49; and N, 6.08.
1H(500MHz，DMSO)δ：1.16(t，6H，J＝6.94Hz)1.66～1.73(m，2H)1.97～2.03(m，2H)2.50(t，2H，J＝6.90Hz)3.43(q，4H，J＝6.92Hz)4.84(t，2H，J＝7.34Hz)6.24(d，1H，J＝2.01Hz)6.39(d，1H，J＝9.06Hz)7.86(d，1H，J＝9.05Hz)7.89～7.97(m，2H)8.11～8.18(m，2H)8.30(d，1H，J＝15.40Hz)8.44(d，1H，J＝8.96Hz)8.83(d，1H，J＝8.55Hz)8.98(d，1H，J＝6.69Hz)10.35(s，1H)。
IR(cm-1)：3380，2972，2926，1571，1541，1525，1412，1271，1211，1178，1108，1048，1029，962。
Example 18: 3, 3-dimethyl-N- (4-sulfonatobutyl) -2- [2- (4-N, N-dimethylaminophenyl)
Vinyl radical]Synthesis of Indoline salt (Dye-18)
Synthesized as described in example 13, except that 2, 3, 3-trimethylindole was used instead of 4-methylpyridine. After purification by column chromatography (silica gel column, methanol: chloroform: 1: 10), the title compound was obtained as a violet solid (0.200 g) in 47% yield. m.p.221-2 ℃.
Elemental analysis C24H30N2O3S: calculated values: c, 67.58; h, 7.09; n, 6.57. measurement：C，67.79；H，6.86；N，6.74。
1H(500MHz，DMSO)δ：1.75(s，6H)1.80～1.83(m，2H)1.90～1.93(m，2H)2.56(t，2H，J＝7.08Hz)3.17(s，6H)4.52(t，2H，J＝7.28Hz)6.88(d，2H，J＝7.89Hz)7.36(d，1H，J＝15.61Hz)7.47(t，1H，J＝7.58Hz)7.54(t，1H，J＝7.45Hz)7.76～7.78(m，2H)8.14(d，2H，J＝7.80Hz)8.33(d，1H，J＝15.57Hz)。
IR(cm-1)：2972，2923，1613，1577，1525，1431，1357，1258，1161，1026，965，773，716，523。
Example 19: 3, 3-dimethyl-N- (4-sulfonatobutyl) -2- [2- (4-N, N-diethylamino-2-hydroxy)
Phenyl) ethenyl]Synthesis of Indoline salt (Dye-19)
Prepared as described in example 18, except that 2-hydroxy-4-N, N-diethylaminobenzaldehyde is used instead of 4-N, N-dimethylaminobenzaldehyde. After purification by column chromatography (silica gel column, methanol: chloroform: 1: 10), the title compound was obtained as a purple solid (0.202 g, 43% yield). m.p.213-4 ℃.
Elemental analysis C26H34N2O4S: calculated values: c, 66.36; h, 7.28; n, 5.95. measurement: c, 66.61; h, 7.48; and N, 6.13.
1H(500MHz，DMSO)δ：1.18(t，6H，J＝7.09Hz)1.69(s，6H)1.77～1.82(m，2H)1.86～1.92(m，2H)2.55(t，2H，J＝7.34Hz)3.50(q，4H，J＝7.09Hz)4.37(t，2H，J＝6.85Hz)6.26(d，1H，J＝2.20Hz)6.51(dd，1H，J＝9.29，2.20Hz)7.25(s，1H)7.40(t，1H，J＝7.58Hz)7.50(t，1H，J＝7.83Hz)7.68(d，1H，J＝8.31Hz)7.71(d，1H，J＝7.34Hz)8.05(s，1H)8，43(d，1H，J＝13.69Hz)11.11(s，1H)。
IR(cm-1)：3440，2970，2928，1615，1571，1521，1425，1353，1263，1153，1075，1033，959，786，706，682，519。
Example 20: n- (4-sulfonatobutyl) -4- [2- (4-N, N)-dimethylaminophenyl) vinyl group]Benzo (b) is
Synthesis of thiazole inner salt (Dye-20)
Prepared as described in example 13, except that 2-methylbenzothiazole was used instead of 4-methylpyridine. Recrystallization from ethanol gave 0.262g of the title compound as dark red crystals in 63% yield. m.p.>300 ℃.
Elemental analysis C21H24N2O3S2: calculated values: c, 60.55; h, 5.81; n, 6.73. measurement: c, 60.45; h, 5.93; and N, 6.45.
1H(500MHz，DMSO)δ：1.80～1.86(m，2H)1.93～1.99(m，2H)2.56(t，2H，J＝6.60Hz)3.13(s，6H)4.82(t，2H，J＝7.09Hz)6.85(d，2H，J＝8.56Hz)7.68(t，1H，J＝7.40Hz)7.73～7.79(m，2H)7.98(d，2H，J＝8.44Hz)8.08(d，1H，J＝15.15Hz)8.21(d，1H，J＝8.37Hz)8.31(d，1H，J＝7.91Hz)。
IR(cm-1)：2975，1573，1529，1493，1445，1379，1334，1273，1187，1166，1032，942，817，767，512。
Example 21: n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) ethenyl]Benzo (b) is
Synthesis of thiazole inner salt (Dye-21)
Prepared as described in example 20, except that 4-N, N-dimethylaminobenzaldehyde is replaced with 4-N, N-diethylaminobenzaldehyde. Recrystallization from ethanol gave 0.297g of the title compound as dark red crystals, 67% yield. m.p.244-5 ℃.
Elemental analysis C23H28N2O3S2: calculated values: c, 62.13; h, 6.35; n, 6.30. measurement: c, 62.46; h, 6.54; and N, 6.07.
1H(500MHz，DMSO)δ：1.18(t，6H，J＝6.85Hz)1.80～1.86(m，2H)1.92～1.99(m，2H)2.56(t，2H，J＝6.70Hz)3.52(q，4H，J＝6.92 Hz)4.80(t，2H，J＝7.06Hz)6.83(d，2H，J＝8.59Hz)7.65～7.72(m，2H)7.77(t，1H，J＝8.00Hz)7.95(d，2H，J＝8.32Hz)8.06(d，1H，J＝15.09Hz)8.19(d，1H，J＝8.49Hz)8.28(d，1H，J＝8.05Hz)。
IR(cm-1)：2975，1572，1522，1492，1449，1413，1335，1264，1184，1152，1077，1033，818，714，511。
Example 22: n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylamino-2-hydroxyphenyl) ethene
Base of]Synthesis of benzothiazole inner salt (Dye-22)
Prepared as described in example 20, except that 2-hydroxy-4-N, N-diethylaminobenzaldehyde is used instead of 4-N, N-dimethylaminobenzaldehyde. Recrystallization from ethanol gave 0.336g of the title compound as dark purple crystals in 73% yield. m.p.275-6 ℃.
Elemental analysis C23H28N2O4S2: calculated values: c, 59.98; h, 6.13; n, 6.08. measurement: c, 60.02; h, 6.41; and N, 6.10.
1H(500MHz，DMSO)δ：1.17(t，6H，J＝7.09Hz)1.77～1.83(m，2H)1.90～1.96(m，2H)2.55(t，2H，J＝7.09Hz)3.46(q，4H，J＝7.34Hz)4.68(t，2H，J＝7.83Hz)6.21(s，1H)6.45(d，1H，J＝9.54Hz)7.56(d，1H，J＝15.16Hz)7.61(t，1H，J＝7.83Hz)7.72(t，1H，J＝7.58Hz)7.93(d，1H，J＝9.05Hz)8.10～8.20(m，3H)10.83(s，1H)。
IR(cm-1)：3441，2972，1569，1522，1489，1420，1338，1248，1212，1111，1032，962，842，683，510。
Example 23: n- (6-hexanoyl) -4- [2- (4-N, N-dimethylaminophenyl) ethenyl]Bromination of pyridine
Synthesis of substance (Dye-23)
Synthesized by the method of synthesis route I:
(1) preparation of 4- [2- (4-N, N-dimethylaminophenyl) ethenyl]pyridine
4.65g (0.05mol) of 4-methylpyridine and 7.45g (0.05mol) of 4-N, N-dimethylaminobenzaldehyde are dissolved in 40mL of acetic anhydride and, after refluxing for 48h, cooled at room temperature. The pH of the reaction mixture was adjusted to about 13 with 40% NaOH, and a large amount of yellow solid precipitated. The solid was collected by suction filtration and recrystallized from acetone to give 4.96g of 4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridine as pale yellow crystals. The yield was 41%. m.p.243-4 ℃.
1H(500MHz，DMSO)δ：3.06(s，6H)6.78(d，2H，J＝8.86Hz)6.97(d，1H，J＝16.37Hz)7.41～7.46(m，3H)7.52(d，2H，J＝8.77Hz)8.49(d，2H，J＝5.01Hz)。
IR(cm-1)：3021，2893，2810，1596，1585，1521，1484，1445，1359，1215，1189，1171，1121，988，969，944，821，549，521。
(2) Synthesis of N- (6-hexanoyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridinium bromide
0.224g (0.001mol) of the product of the above step and 0.195g (0.001mol) of 6-bromohexanoic acid were dissolved in 30mL of anhydrous ethanol. The reaction temperature was controlled at 50 ℃ and stirred for 24 h. And cooling to room temperature. Suction filtration was carried out, and the obtained solid was purified by column chromatography (silica gel column, methanol: chloroform: 1: 5) to obtain 0.088g of an orange-red solid in 26% yield. m.p.>300 ℃.
Elemental analysis C21H27BrN2O2: calculated values: c, 60.15; h, 6.49; n, 6.68. measurement: c, 60.36; h, 6.61; and N, 6.65.
1H(500MHz，DMSO)δ：1.41～1.47(m，2H)1.69～1.74(m，2H)2.00～2.04(m，2H)2.35(t，2H，J＝7.20Hz)3.11(s，6H)4.47(t，2H，J＝7.35Hz)6.81(d，2H，J＝8.91Hz)7.13(d，1H，J＝15.99Hz)7.64(d，2H，J＝8.89Hz)7.88(d，1H，J＝15.99Hz)8.01(d，2H，J＝6.78Hz)8.62(d，2H，J＝6.78Hz)。
IR(cm-1)：3439(s，b)，1706，1640，1560，1413，1338，1167，1020，806，644，518。
Practice ofExample 24: n- (3-Propioniyl) -4- [2- (4-N, N-dimethylaminophenyl) ethenyl]Pyridine inner salt
Synthesis of (Dye-24)
Synthesized by the method of the synthesis route III.
(1) Preparation of N- (3-propionyloxy) -4-methylpyridine inner salt
0.93g (0.01mol) of 4-methylpyridine and 1.52g (0.01mol) of 3-bromopropionic acid are dissolved in 20mL of toluene and stirred at room temperature for 48 h. And (5) carrying out suction filtration to obtain a white solid.
The solid was dissolved in absolute ethanol, excess anhydrous sodium carbonate was added and stirred at room temperature for 24 h. Ethanol was removed by filtration and rotary evaporation to obtain 1.53g of N- (3-propionyloxy) -4-methylpyridine inner salt as a white solid with a yield of 63%.
1H(500MHz，DMSO)δ：2.52(s，3H)3.04(t，2H，J＝6.34Hz)4.69(t，2H，J＝6.34Hz)7.76(d，2H，J＝6.23Hz)8.59(d，2H，J＝6.23Hz)。
(2) Synthesis of N- (3-propionyloxy) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridine inner salt
0.165g (0.001mol) of the product of the above-described step and 0.149g (0.001mol) of 4-N, N-dimethylaminobenzaldehyde are dissolved in 30mL of absolute ethanol. Refluxing for 24 h. And cooling to room temperature. And (4) carrying out suction filtration, and recrystallizing the obtained solid with ethanol to obtain 0.157g of orange-red solid serving as a target compound, wherein the yield is 53%. m.p.203-4 ℃.
Elemental analysis C18H20N2O2: calculated values: c, 72.95; h, 6.80; n, 9.45. measurement: c, 72.89; h, 6.99; and N, 9.16.
1H(500MHz，DMSO)δ：2.51(t，2H，J＝6.21Hz)3.02(s，6H)4.51(t，2H，J＝6.21Hz)6.79(d，2H，J＝8.72Hz)7.17(d，1H，J＝16.11Hz)7.59(d，2H，J＝8.69Hz)7.89(d，1H，J＝16.09Hz)8.00(d，2H，J＝6.61Hz)8.81(d，2H，J＝6.61Hz)。
IR(cm-1)：3026，1586，1529，1401，1370，1330，1188，1162，1045，946，831，813，545。
Practice ofExample 25: n- (3-Propioniyl) -2- [2- (4-N, N-dimethylaminophenyl) ethenyl]Pyridine inner salt
Synthesis of (Dye-25)
Prepared as described in example 23 or 24, except that 2-methylpyridine was used instead of 4-methylpyridine. Recrystallization from ethanol gave 0.175g of the title compound as an orange solid in 69% yield. m.p.175-6 ℃.
Elemental analysis C18H20N2O2: calculated values: c, 72.95; h, 6.80; n, 9.45. measurement: c, 72.85; h, 6.71; and N, 9.32.
1H(500MHz，DMSO)δ：2.53(t，2H，J＝6.46Hz)3.03(s，6H)4.84(t，2H，J＝6.42Hz)6.78(d，2H，J＝8.97Hz)7.36(d，1H，J＝15.71Hz)7.66～7.72(m，3H)7.90(d，1H，J＝15.64Hz)8.32(t，1H，J＝7.80Hz)8.43(d，1H，J＝8.19Hz)8.85(d，1H，J＝6.18Hz)。
IR(cm-1)：2934，2694，1593，1558，1529，1411，1372，1333，1193，1160，945，814，536。
Example 26: n- (4-sulfonatobutyl) -4- [4- (4-N, N-dimethylaminophenyl) butan-1-yl]
Synthesis of pyridine inner salt (Dye-26)
0.001mol of N- (4-sulfobutyl) -4-methylpyridine inner salt was dissolved in 30mL of absolute ethanol, and 0.001mol4- (N, N-dimethylanilino) acrolein and one drop of piperidine were added. The reaction mixture was refluxed with stirring for 16 h. And cooling to room temperature. The reaction solution was evaporated to about 10mL, and 30mL of anhydrous ether was added and left in the refrigerator overnight. And (4) carrying out suction filtration, and recrystallizing the obtained solid with ethanol to obtain 0.223g of red crystals of the target compound with the yield of 61%. m.p.>300 ℃.
Elemental analysis C21H26N2O3S: calculated values: c, 65.28; h, 6.74; n, 7.25. measurement: c, 65.34; h, 6.59; and N, 7.18.
1H(500MHz，DMSO)：1.58-1.61(m，2H，N+CH2CH2CH2)，1.94-1.98(m，2H，N+CH2CH2)，2.47(t，2H，SCH2，J＝6.54Hz)，2.91(s，6H，N(CH3)2)，4.30(t，2H，N+CH2J ═ 6.85Hz), 6.76(d, 2H, ph-H, J ═ 8.45Hz), 7.13(d, 2H, 2CH ═ 15.84Hz), 7.22(d, 1H, ph-H, J ═ 8.21Hz), 7.31(d, 2H, 2CH ═ 15.99Hz), 7.43(d, 1H, ph-H, J ═ 8.21Hz), 8.00(d, 2H, pyridyl, J ═ 5.99Hz), 8.65(d, 2H, pyridyl, J ═ 6.01 Hz).
Example 27 sensitized solar cell Using a Hemicyanine dye of the invention
1. Preparation of dye-sensitized nanocrystalline semiconductor electrode
The preparation method is disclosed in the documents M.K. Nazeerudin, A.Kay, I.Rodicio, R.Humphry-Baker, E.M ü ller, P.Liska, N.Vlachopoulos, M.Gr _ tzel, J.Am.chem.Soc., 1993, 115, 6382. Wide bandgap semiconductor colloid with the particle size of 1-50 nm is coated on a transparent conductive substrate to form a film, the film is sintered at the temperature of 200-600 ℃ for 15 minutes to 12 hours, and the film is cooled and then heavyRepeating the operation until obtaining the wide-bandgap semiconductor nanocrystalline film with the thickness of 1-50 microns. Wherein the transparent conductive substrate is fluorine-doped tin dioxide conductive glass (purchased from Beijing nonferrous metals research institute). Adding TiO into the mixture2The nanocrystalline film is placed in an oven to be heated at the temperature of 100-250 ℃ for 10-120min, and when the nanocrystalline film is cooled to the temperature of 25-100 ℃, the film is immersed to the concentration of 10-5-10-3Mole/liter dye solution. The time required for sensitization varies depending on the dye, and is usually 2 to 48 hours. After determination of the dye, the concentration and sensitization time used can be readily determined by one of ordinary skill in the art based on routine techniques in the art. For example, for the present invention, 5X 10 is selected at the Dye-1 concentration-4The sensitization time is 8 hours per liter; 2X 10 Dye-26 concentration-3The sensitization time was 15 hours per liter. And after sensitization is finished, taking out the sensitization membrane, washing two surfaces of the membrane by using corresponding solvents, and drying to be tested.
2. Assembly of battery
The redox electrolyte used in dye-sensitized solar cells is typically LiI/I2The solvent is Propylene Carbonate (PC), Ethylene Carbonate (EC) or a mixture of the two according to a certain proportion. In dye-sensitized TiO2And dripping a drop of redox electrolyte solution on the surface of the nanocrystalline thin film. Then a piece of platinized ITO glass is placed on the dye-sensitized TiO2And (4) clamping the film by using a clamp to form the thin-layer sandwich type dye-sensitized solar cell shown in the figure. Wherein the dye-sensitized TiO2The electrode is a working electrode, and the platinum-plated ITO glass is a counter electrode.
3. Photoelectrochemical measurement of a cell
The solar cell was measured according to a conventional three-electrode system, and the irradiation light source was a five-step adjustable 500W xenon lamp (Ushio Electric, Japan) or a 1000W solar simulator (1.5AM) (Oriel, USA). Photocurrent and photovoltage output were measured by a Keithley2400 digital primary meter (Keithley corporation, usa).
The performance parameters of the sensitized solar cell measured by using the hemicyanine dye compound prepared by the invention as a sensitizer according to the above method are shown in the following table:
TABLE 2 Performance parameters of Hemicyanine dyes (Dye-1-Dye-25) sensitized solar cells
Dye Isc/mA cm-2Voc/mV FF □η(％)
Dye-1 7.02 465 0.600 2.48
Dye-2 8.06 435 0.632 2.81
Dye-3 3.83 396 0.633 1.20
Dye-4 3.90 374 0.627 1.43
Dye-5 9.62476 0.640 3.70
Dye-6 11.5 462 0.560 3.72
Dye-7 18.4 460 0.530 5.6
Dye-8 8.20 473 0.568 2.75
Dye-9 7.28 440 0.660 2.64
Dye-10 15.8 487 0.570 5.48
Dye-11 15.0 488 0.550 5.13
Dye-12 21.5 535 0.500 7.20
Dye-13 10.2 473 0.570 3.43
Dye-14 8.28 450 0.650 3.02
Dye-15 10.5 449 0.654 3.90
Dye-18 7.67 434 0.649 2.73
Dye-17 14.5 446 0.58 4.69
Dye-18 11.6 460 0.608 4.06
Dye-19 13.6 448 0.580 4.42
Dye-20 12.2 466 0.550 3.90
Dye-21 12.4 455 0.520 3.67
Dye-22 14.8 468 0.570 4.93
Dye-23 7.15 423 0.613 2.33
Dye-24 13.2 480 0.660 5.23
Dye-25 12.7 525 0.61 5.10
Dye-26 7.2 425 0.603 2.32
Wherein, Isc: short circuit photocurrent, VocOpen circuit photovoltage, FF fill factor, η Total energy conversion efficiency
0.1 mol/l LiI +0.6 mol/l PyI +0.05 mol/l I2(the solvent is PC)
The light intensity is 80mW.cm-2
The positive effects are as follows: the dye-sensitized nanocrystalline solar cell of the invention uses a wide forbidden bandThe semiconductor nanocrystalline film is used as a substrate, and the sensitizing agent is a large conjugated hemicyanine dye with an electron donor-pi conjugated system-electron acceptor (D-pi-A) structure shown in a general formula (I). The hemicyanine Dye with the D-Pi-A structure is easy to generate photoinduced electron transfer and has high electron injection rate, and the hemicyanine Dye with the D-Pi-A structure has a large conjugated structure, so that the organic Dye has high sunlight capture efficiency and good photoelectric conversion efficiency, for example, the ultraviolet visible absorption spectrum of the Dye-7 is given in figure 2, the maximum absorption peak of the ultraviolet visible absorption spectrum is 560nm, and TiO is sensitized by the Dye2The I-V curve (shown in figure 3) of the nanocrystalline solar cell shows that the short-circuit photocurrent is as high as 21.5mA/cm2The conversion efficiency of monochromatic light is up to 100% as can be seen from the photocurrent working spectrum (see fig. 4). The experimental data given in the table above show that the hemicyanine dye sensitizes TiO according to the invention2The total energy conversion efficiency of the nanocrystalline solar cell is higherHigh, nearly one-half of the compounds have conversion rates of nearly 4% or more, with Dye-12 conversion rates as high as 7.20%, which is the highest value reported in the literature for organic Dye sensitizers. Thus, new solar cells with higher efficiency can be produced using such hemicyanine dyes as sensitizers.
Claims (17)
1. A compound having an internal salt or onium salt of a nitrogen-containing heterocycle of the formula (I):
D-π-A-Q-G
wherein
The linking group Q is an alkylene group having 1 to 20 carbon atoms;
the bonding group G being a sulfonate group SO3 -Carboxyl COOH or carboxylate group CO2 -；
A group pi is an alkenylene group capable of forming a conjugate with the groups D and a;
the electron donor group D is one of the following groups:
wherein R isDIs one or more, preferably one or two hydroxyl groups,
RD1is a straight or branched alkyl group having 1 to 20 carbon atoms;
the electron acceptor group a is a large conjugated group of one of the following groups:
wherein
A1-A4 is linked to the Q group at the position of the quaternary nitrogen atom and to the pi group at another bonding position, and
the attachment positions of A1 and A2 to the π group are ortho or para to the position of the attachment Q group,
B1is an N or C atom, and the compound is,
B2is an O, N, S or Catom, and has the following structure,
RAis hydrogen, one or more of having 1 to 4 carbon atomsStraight or branched chain alkyl or alkoxy radicals of the formulae
RA1Is a straight chain alkyl group having 1 to 4 carbon atoms;
with the proviso that when B2When N is, optionally one RA1A group; when B is present2When C is present, it may optionally have one or two RA1A group; when B is present2When O and S are present, no R is presentA1A group.
2. A compound according to claim 1 wherein the linking group Q is an alkylene group having 2 to 6 carbon atoms.
3. A compound according to claim 2 wherein the linking group Q is an alkylene group having 3 or 4 carbon atoms.
4. A compound according to claim 1, wherein the groups are vinylidene and 1, 4-butadienyl.
5. A compound according to claim 4, wherein the group π is vinylene.
6. A compound according to claim 1, wherein the electron donor group D is the aniline group of D2.
7. A compound according to claim 1 wherein the electron donor group D is hydroxy substituted.
8. A compound according to claim 1 wherein the electron acceptor group a is a 4.
9. The compound according to claim 1, wherein the compound is an electronacceptor group a is a4 and the bonding group G is a sulfonate group SO3 -The compound of (1).
10. The compound according to claim 1, wherein the compound is such that the electron acceptor group a is a1 and the bonding group G is a carboxylate group CO2 -The compound of (1).
11. The compound according to claim 1, wherein the compound is selected from the group consisting of:
n- (3-sulfopropyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridinium inner salt (Dye-1),
n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) vinyl]pyridine inner salt (Dye-2),
1- (3-sulfopropyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyrimidinium inner salt (Dye-3),
1- (3-sulfopropyl) -4- [2- (4-N, N-diethylaminophenyl) vinyl]pyrimidineinner salt (Dye-4),
3, 3-dimethyl-N- (3-sulfonatopropyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]naphtho [1, 2-d]pyrrole inner salt (Dye-5),
3, 3-dimethyl-N- (3-sulfonatopropyl) -2- [2- (4-N, N-diethylaminophenyl) vinyl]naphtho [1, 2-d]pyrrole inner salt (Dye-6),
3, 3-dimethyl-N- (3-sulfopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]naphtho [1, 2-d]pyrrol inner salt (Dye-7),
n- (3-sulfopropyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]benzoxazole inner salt (Dye-8),
n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) vinyl]benzoxazole inner salt (Dye9),
n- (3-sulfopropyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]- β -naphthothiazole inner salt (Dye-10),
n- (3-sulfopropyl) -2- [2- (4-N, N-diethylaminophenyl) vinyl]- β -naphthothiazole inner salt (Dye-11),
n- (3-sulfopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]- β -naphthothiazole inner salt (Dye-12),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridine inner salt (Dye-13),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) vinyl]pyridine inner salt (Dye-14),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]quinoline inner salt (Dye-15),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) vinyl]quinoline inner salt (Dye-16),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]quinoline inner salt (Dye-17),
3, 3-dimethyl-N- (4-sulfonatobutyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]indolium salt (Dye-18),
3, 3-dimethyl-N- (4-sulfonatobutyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]indolium salt (Dye-19),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]benzothiazole inner salt (Dye-20),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylaminophenyl) vinyl]benzothiazole inner salt (Dye-21),
n- (4-sulfonatobutyl) -4- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]benzothiazole inner salt (Dye-22),
n- (6-hexanoyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridinium bromide (Dye-23),
n- (3-Propioniyl) -4- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridine inner salt (Dye-24),
n- (3-propanoyl) -2- [2- (4-N, N-dimethylaminophenyl) vinyl]pyridine inner salt (Dye-25), and
n- (4-sulfonatobutyl) -4- [4- (4-N, N-dimethylaminophenyl) butan-1-yl]pyridine inner salt (Dye-26).
12. The compound according to claim 8, wherein the preferred compound is N- (3-sulfopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]- β -naphthothiazole inner salt (Dye-12).
13. A process for the preparation of a compound according to any one of claims 1 to 9, wherein the compound in which the group pi is vinylidene can be synthesized by the following synthetic route:
wherein the D, A, Q and G groups are as defined in claim 1;
the nitrogen-containing heterocyclic compound of the methyl-substituted receptor group A and benzaldehyde derivative are subjected to condensation reaction in acetic anhydride under the heating condition to prepare a corresponding large conjugated system, and then the large conjugated system is reacted with corresponding substituted carboxylic acid or sulfonic acid to prepare the required target product.
14. A process for the preparation of a compound according to any one of claims 1 to 9, wherein the bonding group G is a sulfonate group SO3 -And Q1Compounds which are alkylene having 3 to 4 carbon atoms can be prepared according to the following synthetic routes:
wherein Q1 is alkylene having 3 or 4 carbon atoms, the D, A and G groups are as defined in claim 1;
the nitrogen-containing heterocyclic compound of methyl-substituted acceptor group A and sultone react in organic solvent in the presence of small amount of hexahydropyridine under heating condition, and the obtained product and corresponding aldehyde react in organic solvent under heating condition to obtain the required target product.
15. Process for the preparation of a compound according to any one of claims 1 to 9, wherein the bonding group G is a carboxylate group CO2 -The compounds of (a) can be prepared according to the following synthetic routes:
wherein X is a conventional leaving group, D, A and the Q group are as defined in claim 1;
the nitrogen-containing heterocyclic compound of methyl-substituted receptor group A and substituted carboxylic acid are reacted in an organic solvent in the presence of a small amount of piperidine under the heating condition, and the obtained product is heated and reacted with equimolar corresponding aldehyde in the organic solvent to prepare the required target product.
16. A nanocrystalline semiconductor solar cell, wherein a compound according to any one of claims 1 to 12 is used as sensitizer.
17. The nanocrystalline semiconductor solar cell of claim 16, wherein the sensitizer is N- (3-sulfonatopropyl) -2- [2- (4-N, N-diethylamino-2-hydroxyphenyl) vinyl]- β -naphthothiazole inner salt.
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