CN103540157B - Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof - Google Patents

Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof Download PDF

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CN103540157B
CN103540157B CN201310525241.3A CN201310525241A CN103540157B CN 103540157 B CN103540157 B CN 103540157B CN 201310525241 A CN201310525241 A CN 201310525241A CN 103540157 B CN103540157 B CN 103540157B
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dye
benzoglyoxaline
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pyridine
metal complexes
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CN103540157A (en
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钟超凡
章伟
唐桂鹏
周俊
彭大海
胡娇梅
谢秋芳
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Xiangtan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses a polymeric metal-complex functional dye containing a 2-(2'-pyridyl)benzimidazole D-pi-A type structure and a preparation method thereof. According to the molecular structure of the dye, a large-pi conjugate system is formed through taking carbazole derivatives and alkoxy phenyl as donors (D), taking thiophene vinyl as pi bridges and taking metal complexes of 2-(2'-pyridyl)benzimidazole as receptors (A), and then, the photoelectric conversion efficiency of dye-sensitized solar cells is increased. The dye and the preparation method thereof have the advantage that the novel dye with high photovoltaic performance, low cost and high stability is obtained through reasonably integrating inorganic molecules, organic molecules and macromolecules. Ordinary transition-metal complexes are selected to replace complexes of rare-precious metals, such as ruthenium and the like, so that the cost of the dye is reduced; shown by tests, the prepared dye embodies good photoelectric conversion performance and high thermal stability, so that the dye has a great application prospect in the aspect of the exploitation and utilization of energy sources and can be applied to the dye-sensitized solar cells.

Description

One class contains D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline and preparation method thereof
Technical field
The present invention relates to one and there is D-π-A type topology convergence metal complexes functional dye and preparation method thereof, belong to photoelectric material and field of new.
Background technology
Dye sensitization solar battery is and O ' Regan 1991 research invention.Its photovoltaic principle is as follows: by being adsorbed on battery FTO glass pole plate upper film TiO 2the dye sensitizing agent of particle surface absorbs sunlight, and dye-sensitized molecules excites, and excited state electronics is by the TiO of sensitization 2after film transfer to FTO glass electrode, electronics by external circuit be transferred to battery to (just) electrode (Pt or Al), and then the excited state of dye-sensitized molecules is transferred to by the redox electrolytes matter in battery, make it get back to ground state, realize a photoelectric conversion process.
Dye sensitization solar battery mainly imitates photosynthesis principle; the novel solar cell of the one developed; its main advantage is: abundant raw materials, with low cost, Technology is simple; in big area suitability for industrialized production, there is larger advantage; and nearly all starting material and production technique are all nontoxic pollution-frees; portion of material can also reclaim, to the development of new forms of energy and the protection of human environment significant.
In recent years, the research of pure organic dye obtained and developed rapidly, and cell conversion efficiency have also been obtained raising.The dye sensitizing agent that cost of development is low, level-density parameter, stable performance, spectral absorption are mated with sunlight is current development trend; But the technical problem underlying that the permanent stability of electricity conversion, big area, battery are dye sensitization solar batterys to be faced.
2-(2 '-pyridine) benzoglyoxaline has large rigid structure, coordination can be carried out with a lot of metal, and carbazole derivative and alkoxy benzene are extraordinary donor materials, the polymer-metal complex that they are formed has larger pi-conjugated structure, not only be beneficial to hole transport and the electric transmission of polymer-metal complex, and there is high stability, contribute to improving dyestuff electricity conversion and work-ing life.
Summary of the invention
The object of the invention is D-π-A type topology convergence metal complexes functional dye providing a class containing 2-(2 '-pyridine) benzoglyoxaline and preparation method thereof, be aggregated in by Heck in the part of 2-(2 '-pyridine) benzimidizole derivatives introduce carbazole derivative or alkoxy benzene to body, form the polymer-metal complex functional dye of D-π-A structure, application and dye sensitization solar battery.
Technical scheme of the present invention is: a class is containing the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline, and this compound has D-π-A structure, and its general formula is as follows:
In formula, L is: CH 3cOO -, Cl -; M is: metal ion Co (II), the Cu (II) of subgroup, Zn (II), Cd (II) or Ni (II); N is the polymerization degree: the integer of 5 ~ 10; D is selected from alkoxy benzene or carbazole derivative, and its structural formula is:
One class is containing the preparation method of the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline:
(1) preparation of .2-(2 '-pyridine) benzoglyoxaline: in a reservoir, adds O-Phenylene Diamine and 2-pyridine carboxylic acid that equivalence ratio is 1: 1, and polyphosphoric acid is as solvent, and stir, under nitrogen protection, oil bath is heated to 160-180 DEG C; Heating 4 ~ 6h, pours into mixture in frozen water and cools, with NaOH regulator solution pH=6 ~ 8; By sedimentation and filtration, dry, crude product is recrystallization in methanol solution, obtains pale solid 2-(2 '-pyridine) benzoglyoxaline;
(2) preparation of the bromo-5-of .2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene: get 2 respectively, the bromo-3 methyl thiophene of 5-bis-, 2-(2 '-pyridine) benzoglyoxaline, cupric iodide, salt of wormwood, 1, 10-phenanthroline ratio is with DMF to dissolve at 1: 1: 0.25: 4: 0.4, join with in magnetic agitation container, under nitrogen protection, oil bath is heated and the 24 ~ 26h that refluxes, liquid to be mixed is cooled to room temperature, the brown solution obtained, extract with chloroformic solution, with anhydrous magnesium sulfate drying, and column chromatography eluting with 1: 1 tetrahydrofuran (THF)/normal hexane, obtain the bromo-5-of brown solid 2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene,
(3). the preparation of metal complexes: be that the bromo-5-of 1 equivalent 2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene is dissolved in methyl alcohol by equivalence ratio, reflux, and when starting to reflux, by in the metal-salt methanol solution of 0.5 equivalent subgroup instillation reactor, the reaction after 12 ~ 14 hours that refluxes stops, filter and use methyl alcohol and ethanolic soln washing, drying obtains metal complexes;
(4) preparation of .1,4-divinyl-2,5-bis-octyloxy benzene: in nitrogen gas stream, joins 60 ~ 100ml CH by the formaldehyde solution of 37% and 2,5-, bis-octyloxies-Isosorbide-5-Nitrae-two (triphenylphosphine brooethyl) benzene 2cl 2in; Then under ice-water bath condition, slowly dripping massfraction is the NaOH solution of 20% ~ 40%, reacts 24 ~ 26h, use CH under room temperature 2cl 2extraction, then wash with water, through MgSO 4dried overnight, filters, and screws out solvent C H 2cl 2, obtain crude product, obtain pure substance with ethyl alcohol recrystallization, dry under vacuum condition, obtain solid product Isosorbide-5-Nitrae-divinyl-2,5-bis-octyloxy benzene of white;
(5) .3, the preparation of 6-divinyl-N-octylcarbazol: get 3,6-diacetyl-N-octylcarbazol and methyl bromide phosphorus ylide salt ratio are be dissolved in anhydrous tetrahydro furan at 1: 2, slowly add sodium hydride, then under the protection of nitrogen, mixture is heated to backflow, and reacts 8 ~ 9 hours; After reaction terminates, mixture cool to room temperature, first slowly add methyl alcohol to mixture, add distilled water more subsequently, and with dichloromethane extraction, anhydrous magnesium sulfate drying spends the night, then extraction liquid is concentrated, with chromatography over CC, with hexanaphthene: ethyl acetate=1: 10 make leacheate, obtain yellow solid 3,6-divinyl-N-octylcarbazol;
(6). by 1,4-divinyl-2,5-bis-octyloxy benzene and 3,6-divinyl-N-octylcarbazol, respectively with metal complexes with 1: 1 ratio join in reaction flask, then add refining triethylamine, three (2-tolyl) phosphine and palladium successively, under logical condition of nitrogen gas, reaction system keeps 90 DEG C, react 24 ~ 26 hours, be cooled to room temperature after reaction terminating, filter, with methanol extraction, then the crude product obtained is dissolved in tetrahydrofuran (THF), be precipitation again with methyl alcohol, filter, under vacuum condition, drying obtains polymer-metal complex.
One class, containing the purposes of the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline, is used as dye sensitizing agent in dye sensitization solar battery.
The main advantage of invention is: a kind of D-π-A type topology convergence metal complexes containing 2-(2 '-pyridine) benzoglyoxaline, by organometallic complex polymerization, to expand the large π system of complex molecule, improve its photo absorption performance and carrier transport ability; The common B metal such as research zinc replaces noble ruthenium synthesized polymer metal complex dye, greatly will reduce sensitization solar battery cost and former resource limit.
Accompanying drawing explanation
Nucleus magnetic hydrogen spectrum (400MHz, the CDCl of Fig. 1 embodiment of the present invention synthesis 2-(2 '-pyridine) benzoglyoxaline 3, TMS);
2-(2 '-pyridine) benzoglyoxaline synthesized by Fig. 2 embodiment of the present invention meets nucleus magnetic hydrogen spectrum (400MHz, the CDCl of thiophene 3, TMS);
Fig. 3 embodiment of the present invention synthesizedization is containing nucleus magnetic hydrogen spectrum (400MHz, the CDCl of the metal complexes of zine ion 3, TMS);
Nucleus magnetic hydrogen spectrum (400MHz, the CDCl of Isosorbide-5-Nitrae-divinyl-2,5-bis-octyloxy benzene synthesized by Fig. 4 embodiment of the present invention 3, TMS);
The compound L 1 that Fig. 5 embodiment of the present invention obtains, infrared spectra (KBr crystal compressing tablet, the 4000 ~ 450cm of P1, P3 -1);
The compound L 2 that Fig. 6 embodiment of the present invention obtains, infrared spectra (KBr crystal compressing tablet, the 4000 ~ 450cm of P2, P4 -1);
The TGA curve of the compound P1 ~ P4 synthesized by Fig. 7 the invention process;
The normalized uv-visible absorption spectroscopy of the compound P1 ~ P4 synthesized by Fig. 8 the invention process;
The battery J-V curve of the compound P1 ~ P4 synthesized by Fig. 9 the invention process;
The battery IPCE curve of the compound P1 ~ P4 synthesized by Figure 10 the invention process.
Embodiment
The reaction mechanism of compound of the present invention is:
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1:
One class contains zinc ion coordination thing (P1) containing the D-π-A type topology convergence of 2-(2 '-pyridine) benzoglyoxaline
A kind of using alkoxy benzene as giving body (D), L is CH 3cOO -, M is Zn, and polymerization degree n is the compound (P1) of 7, and its molecular structural formula is:
The preparation method of above-mentioned polymer-metal complex P1:
A.2-the preparation of (2 '-pyridine) benzoglyoxaline: be full of in the there-necked flask of nitrogen with whipping appts, add O-Phenylene Diamine 5.48g (0.05mol) and 2-pyridine carboxylic acid 8.9g (0.07mol), polyphosphoric acid 38.3g, oil bath is heated to 180 DEG C.After heating 4h, mixture is poured in 100mL frozen water and cool, with NaOH regulator solution pH=8.By sedimentation and filtration, dry, crude product is recrystallization in methanol solution, obtains pale solid 2-(2 '-pyridine) benzoglyoxaline 6.68g (productive rate: 67.6% characterizes as shown in Figure 1).
B.2-the preparation of bromo-5-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene: get 2 respectively, bromo-3 methyl thiophene (the 1.27g of 5-bis-, 5.0mmol), 2-(2 '-pyridine) benzoglyoxaline (0.99g, 5.0mmol), cupric iodide (0.08g, 0.43mmol), salt of wormwood (1.38g, 8.9mmol), 1, 10-phenanthroline (0.16g, 0.88mmol) dissolve with 5mL DMF, join with magnetic stirring apparatus and mix with in the there-necked flask of nitrogen protection device, oil bath is heated and the 24h that refluxes, liquid to be mixed is cooled to room temperature, the brown solution chloroformic solution obtained extracts, with anhydrous magnesium sulfate drying, and with column chromatography (1: 1 tetrahydrofuran (THF)/normal hexane) purifying, obtain the bromo-5-of brown solid 2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene 0.74g (productive rate: 40.2%, characterize as shown in Figure 2).
C. the preparation of zine ion metal complexes: the compound 0.74g (2mmol) obtained by B is dissolved in methyl alcohol, reflux, and will containing in the methanol solution instillation reactor of two water zinc acetate 0.22g (1mmol) when starting to reflux, the reaction after 12 hours that refluxes stops, filter and use methyl alcohol and ethanolic soln washing, drying obtains metal complexes (L1) 0.42g (productive rate: 80%, Infrared Characterization as shown in Figure 5) containing zine ion.
D.1, the preparation of 4-divinyl-2,5-bis-octyloxy benzene: in nitrogen gas stream, joins 60ml CH by the formaldehyde solution of 20ml 37% and 2,5-, bis-octyloxies-Isosorbide-5-Nitrae-two (triphenylphosphine brooethyl) benzene (4.3064g, 4.5mmol) 2cl 2in.Then under ice-water bath condition, slowly dripping 40mL massfraction is the NaOH solution of 20%, reacts 24 hours, use CH under room temperature 2cl 2extract three times, then wash with water, through MgSO 4dried overnight, filters, and screws out solvent C H 2cl 2, obtain crude product, obtain pure substance with ethyl alcohol recrystallization, dry under vacuum condition, obtain solid product Isosorbide-5-Nitrae-divinyl-2,5-bis-octyloxy benzene (productive rate: 69% characterizes as shown in Figure 3) of 1.4g white.
E., in the flask of 25ml, Isosorbide-5-Nitrae-divinyl-2 is added successively, 5-bis-(octyloxy) benzene (0.122g, 0.315mmol), title complex L1 (0.173g, 0.315mmol), dry refining DMF (8ml), palladium (0.0029g, 0.013mmol), three (2-tolyl) phosphine (0.022g, 0.072mmol), triethylamine (3mL).Vacuumize logical nitrogen protection; control temperature 90 DEG C reaction 24 hours, cooling, filters; with methanol extraction; filter to obtain crude product, crude product tetrahydrofuran (THF) is dissolved, uses methanol extraction again; filter; vacuum-drying, obtains D-π-A type topology convergence Zn complex (P1) 0.184g (productive rate: 53%, Infrared Characterization as shown in Figure 5) of ruddy solid one containing 2-(2 '-pyridine) benzoglyoxaline.
Embodiment 2
A kind of D-π-A type topology convergence containing 2-(2 '-pyridine) benzoglyoxaline is containing cobalt ion title complex (P2)
A kind of using alkoxy benzene as giving body (D), L is CH 3cOO -(Ac -), M is Co, and polymerization degree n is the compound (P2) of 10, and its molecular structural formula is:
The synthesis of above-mentioned polymer-metal complex P2:
Steps A, B, D are consistent with the synthetic method of A, B, D in embodiment 1.
C: the synthesis containing the metal complexes of cobalt ion: the synthetic method of the metal complexes containing zine ion in method and embodiment 1 is similar, just 0.22g bis-water zinc acetate is become 0.17g bis-water cobaltous acetate, must containing metal complexes (L2) 0.41g (productive rate: 82%, Infrared Characterization as shown in Figure 6) of cobalt ion.
E: similar with the step e in embodiment 1, only have the title complex L1 (0.173g of centre, 0.315mmol) become title complex L2 (0.157g, 0.315mmol), obtain the D-π-A type topology convergence of solid one containing 2-(2 '-pyridine) benzoglyoxaline containing cobalt ion title complex (P2) 0.174g (productive rate: 51%, Infrared Characterization as shown in Figure 6).
Embodiment 3
A kind of D-π-A type topology convergence containing 2-(2 '-pyridine) benzoglyoxaline is containing zinc ion coordination thing (P3)
Using carbazole derivative as giving body (D), L is CH 3cOO -, M is Zn, and polymerization degree n is the compound (P3) of 8, and its molecular structural formula is:
The synthesis of above-mentioned polymer-metal complex P3:
Steps A, B, C are consistent with the synthetic method of A, B, C in embodiment 1.
D:3; the preparation of 6-divinyl-N-octylcarbazol: get 2.2g3; 6-diacetyl-N-octylcarbazol and 5.2g methyl bromide phosphorus ylide salt are dissolved in 70mL anhydrous tetrahydro furan; slowly add 0.8g sodium hydride; then under the protection of nitrogen; mixture is heated to backflow, and reacts 8 hours.After reaction terminates, mixture cool to room temperature, first slowly add 100mL methyl alcohol to mixture, add 100mL distilled water more subsequently, and with dichloromethane extraction, anhydrous magnesium sulfate drying spends the night, then extraction liquid is concentrated, with chromatography over CC (hexanaphthene: ethyl acetate=1: 10 make leacheate), obtain yellow solid (productive rate: 60% characterizes as shown in Figure 4).
E: similar with the step e in embodiment 1, only have 1 of centre, 4-divinyl-2,5-bis-(octyloxy) benzene (0.122g, 0.315mmol) become 3,6-divinyl-N-octylcarbazol (0.104g, 0.315mmol), obtain the D-π-A type topology convergence of solid one containing 2-(2 '-pyridine) benzoglyoxaline containing zinc ion coordination thing (P3) 0.195g (productive rate: 62%, Infrared Characterization as shown in Figure 5).
Embodiment 4
A kind of D-π-A type topology convergence containing 2-(2 '-pyridine) benzoglyoxaline is containing cobalt ion title complex (P4)
Using carbazole derivative as giving body (D), L is CH 3cOO -(Ac -), M is Co, and polymerization degree n is the compound (P3) of 8, and its molecular structural formula is:
The synthesis of above-mentioned polymer-metal complex P4:
Steps A, B are consistent with the synthetic method of A, B in embodiment 1; Step C is consistent with the C in embodiment 2; Step D is consistent with the D in embodiment 3.
E: similar with the step e in embodiment 1, only have and the title complex L1 (0.173g, 0.315mmol) of centre is become title complex L2 (0.157g, 0.315mmol), 1,4-divinyl-2,5-bis-(octyloxy) benzene (0.122g, 0.315mmol) becomes 3,6-divinyl-N-octylcarbazol (0.104g, 0.315mmol), solid P40.168g (productive rate: 48%, Infrared Characterization as shown in Figure 6) is obtained.
Here is four kinds of polymer-metal complex Dyes structural formulae that embodiment 1 ~ 4 is synthesized, and table one is their photovoltaic performance result, and thermal performance test and photovoltaic performance test are as shown in Fig. 7 ~ 10

Claims (3)

1. a class is containing the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline, and it is characterized in that, this compound has D-π-A structure, and its general formula is as follows:
In formula, L is: CH 3cOO -, Cl -; M is: metal ion Co (II), the Cu (II) of subgroup, Zn (II), Cd (II) or Ni (II); N is the polymerization degree: the integer of 5 ~ 10; D is selected from alkoxy benzene or carbazole derivative, and its structural formula is:
2. a class according to claim 1 is containing the preparation method of the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline:
(1) preparation of .2-(2 '-pyridine) benzoglyoxaline: in a reservoir, adds O-Phenylene Diamine and 2-pyridine carboxylic acid that equivalence ratio is 1: 1, and polyphosphoric acid is as solvent, and stir, under nitrogen protection, oil bath is heated to 160 ~ 180 DEG C; Heating 4 ~ 6h, pours into mixture in frozen water and cools, with NaOH regulator solution pH=6 ~ 8; By sedimentation and filtration, dry, crude product is recrystallization in methanol solution, obtains pale solid 2-(2 '-pyridine) benzoglyoxaline;
(2) preparation of the bromo-5-of .2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene: get 2 respectively, the bromo-3 methyl thiophene of 5-bis-, 2-(2 '-pyridine) benzoglyoxaline, cupric iodide, salt of wormwood, 1, 10-phenanthroline ratio is with DMF to dissolve at 1: 1: 0.25: 4: 0.4, join with in magnetic agitation container, under nitrogen protection, oil bath is heated and the 24 ~ 26h that refluxes, liquid to be mixed is cooled to room temperature, the brown solution obtained, extract with chloroformic solution, with anhydrous magnesium sulfate drying, and column chromatography eluting with 1: 1 tetrahydrofuran (THF)/normal hexane, obtain the bromo-5-of brown solid 2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene,
(3). the preparation of metal complexes: be that the bromo-5-of 1 equivalent 2-[(2 '-pyridyl) benzoglyoxaline]-3 methyl thiophene is dissolved in methyl alcohol by equivalence ratio, reflux, and when starting to reflux, by in the metal-salt methanol solution of 0.5 equivalent subgroup instillation reactor, the reaction after 12 ~ 14 hours that refluxes stops, filter and use methyl alcohol and ethanolic soln washing, drying obtains metal complexes;
(4) preparation of .1,4-divinyl-2,5-bis-octyloxy benzene: in nitrogen gas stream, joins 60 ~ 100ml CH by the formaldehyde solution of 37% and 2,5-, bis-octyloxies-Isosorbide-5-Nitrae-two (triphenylphosphine brooethyl) benzene 2cl 2in; Then under ice-water bath condition, slowly dripping massfraction is the NaOH solution of 20% ~ 40%, reacts 24 ~ 26h, use CH under room temperature 2cl 2extraction, then wash with water, through MgSO 4dried overnight, filters, and screws out solvent C H 2cl 2, obtain crude product, obtain pure substance with ethyl alcohol recrystallization, dry under vacuum condition, obtain solid product Isosorbide-5-Nitrae-divinyl-2,5-bis-octyloxy benzene of white;
(5) .3, the preparation of 6-divinyl-N-octylcarbazol: get 3,6-diacetyl-N-octylcarbazol and methyl bromide phosphorus ylide salt ratio are be dissolved in anhydrous tetrahydro furan at 1: 2, slowly add sodium hydride, then under the protection of nitrogen, mixture is heated to backflow, and reacts 8 ~ 9 hours; After reaction terminates, mixture cool to room temperature, first slowly add methyl alcohol to mixture, add distilled water more subsequently, and with dichloromethane extraction, anhydrous magnesium sulfate drying spends the night, then extraction liquid is concentrated, with chromatography over CC, with hexanaphthene: ethyl acetate=1: 10 make leacheate, obtain yellow solid 3,6-divinyl-N-octylcarbazol;
(6). by 1,4-divinyl-2,5-bis-octyloxy benzene and 3,6-divinyl-N-octylcarbazol, respectively with metal complexes with 1: 1 ratio join in reaction flask, then add refining triethylamine, three (2-tolyl) phosphine and palladium successively, under logical condition of nitrogen gas, reaction system keeps 90 DEG C, react 24 ~ 26 hours, be cooled to room temperature after reaction terminating, filter, with methanol extraction, then the crude product obtained is dissolved in tetrahydrofuran (THF), be precipitation again with methyl alcohol, filter, under vacuum condition, drying obtains polymer-metal complex.
3. a class according to claim 1 is containing the purposes of the D-π-A type topology convergence metal complexes functional dye of 2-(2 '-pyridine) benzoglyoxaline, in dye sensitization solar battery, be used as dye sensitizing agent.
CN201310525241.3A 2013-10-31 2013-10-31 Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof Expired - Fee Related CN103540157B (en)

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