CN106189363A - One class closes polymer-metal complex dye sensitizing agent of Cd (II) and its production and use containing 2 (2 ' hydroxy phenyl) benzimidizole derivatives - Google Patents
One class closes polymer-metal complex dye sensitizing agent of Cd (II) and its production and use containing 2 (2 ' hydroxy phenyl) benzimidizole derivatives Download PDFInfo
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- CN106189363A CN106189363A CN201610503672.3A CN201610503672A CN106189363A CN 106189363 A CN106189363 A CN 106189363A CN 201610503672 A CN201610503672 A CN 201610503672A CN 106189363 A CN106189363 A CN 106189363A
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- Prior art keywords
- bromo
- metal complex
- benzimidizole derivatives
- phenol
- benzimidazolyl
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 14
- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 14
- 239000000434 metal complex dye Substances 0.000 title claims description 8
- 125000004464 hydroxyphenyl group Chemical group 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229930192474 thiophene Natural products 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000975 dye Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000004696 coordination complex Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002220 fluorenes Chemical class 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 3
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical group C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 241001597008 Nomeidae Species 0.000 abstract description 5
- 125000005605 benzo group Chemical group 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- -1 alpha-cyanoacrylate 8 hydroxyquinoline Chemical compound 0.000 abstract 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910014568 C—O-M Inorganic materials 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- XWXMGTIHBYFTIE-UHFFFAOYSA-N chembl203360 Chemical compound OC1=CC=CC=C1C1=NC2=CC=CC=C2N1 XWXMGTIHBYFTIE-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- 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
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
D A ' π A type polymer-metal complex new dye sensitizer closing Cd (II) containing 2 (2 ' hydroxy phenyl) benzimidizole derivatives that the present invention relates to a class such as formula I and preparation method thereof and the application in DSSC.This dye-sensitized molecules is using benzo two thiophene derivant (BDTT) or fluorene derivative (FL) as donor (D), benzimidizole derivatives closes the coordination compound of Cd (II) as auxiliary electron receptor (A '), assistant ligand alpha-cyanoacrylate 8 hydroxyquinoline of Cd (II) is as π bridge and main electron acceptor (A), by Yamamoto polyreaction, obtain such two kinds of dye sensitizing agent PBDTT BP Cd and PFL BP Cd.Advantage of the invention is that design and be prepared for that inorganic, organic and macromolecule are rationally combined together by a class, new D A ' π A type polymerization Cd (II) complex dye sensitizer, its photovoltaic application test result shows that it has higher photovoltaic performance, low cost and good heat stability, has bigger application prospect in terms of energy exploitation and application.
Description
Technical field
The present invention relates to a class and close the polymer-metal complex of Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
Dye sensitizing agent and its production and use, belongs to solar cell material and field of functional materials.
Background technology
DSSC has constantly made progress since research invention in 1991 at Gr tzel and O ' Regan,
Have become as and the most potential utilize one of renewable technology with clean energy resource.DSSC is mainly
Imitate photosynthesis principle, the novel solar cell of one developed, its main advantage is: abundant raw materials, with low cost,
Technology is simple, has bigger advantage in large area industrialized production, and nearly all raw material and production technology
Being all low toxicity of low pollution, portion of material can also reclaim, and the development of new forms of energy and the protection of human environment are had important meaning
Justice.
Dye sensitizing agent (abbreviation dyestuff) is the most critical activity composition affecting DSSC photovoltaic performance
Part, carry absorption sunlight to produce electronics and to transmit the most important functions of electronics, therefore research synthesize high photovoltaic performance,
Low cost, high stability new dye significant.
The dyestuff of D-A '-π-A structure is compared with the dyestuff of traditional D-π-A structure: introduce extra accessory receptor, strengthens
The spectral response of dyestuff, and make the light absorption range move to long wave direction；π bridge between accessory receptor and main receptor is at transmission electricity
While son, moreover it is possible to stop and be transmitted to TiO2The electronics of thin film is combined with the positive charge in donor direction；Experiment shows, have D-A '-
The dyestuff of π-A structure is generally of more preferable light, heat stability and higher optical-electronic conversion efficiency compared with D-π-A structure.
In this patent, 2-(2 '-hydroxy phenyl) benzimidizole derivatives has big rigid structure, can enter with a lot of metals
Row coordination；Benzo two thiophene derivant and fluorene derivative are extraordinary donor materials, and the polymer-metal complex formed
There is hole transport and the electric transmission of bigger pi-conjugated structure, beneficially polymer-metal complex；Donor and part draw
Enter long alkyl chain, add the dissolubility of polymer-metal complex dyestuff；Metal Cd (II) is risen by the coordinate bond between part
Draw electronic action, as accessory receptor, due to the Intramolecular electron transfer between itself and part, add the photon absorbing intensity of dyestuff；
8-hydroxyquinoline is positioned between Cd (II) accessory receptor and the conventional alpha-cyanoacrylate with carboxyl grappling base, as π bridge, with
While metal-complexing, play and stop electronics compound and increase the effect of conjugated system.
By above design, contribute to obtaining optical-electronic conversion efficiency height, the new dye of good stability, be dye sensitization
It solaode is an important new direction of dye sensitizing agent development.
Summary of the invention
It is an object of the invention to provide a class cries out 2-(2 '-hydroxy phenyl) benzimidizole derivatives to close the polymerization of Cd (II)
Metal complex dye sensitizer and preparation method thereof and the application in high-performance DSSC.Pass through
Yamamoto is aggregated in the part of benzimidizole derivatives introducing benzo two thiophene derivant or fluorene derivative donor, synthesizes two
Polymer-metal complex PBDTT-BP-Cd and PFL-BP-Cd of individual D-A '-π-A structure, and it is applied to dye sensitization of solar electricity
Dye sensitizing agent is done in pond.
The technical scheme is that a class closes the polymerization of Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
Metal complex, it is characterised in that this compound has D-A '-π-A structure, its formula such as formula I:
Formula I.
One class closes the D-A '-π-A type polymer-metal complex of Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
The preparation method of PBDTT-BP-Cd and PFL-BP-Cd.
(1) preparation of the bromo-2-of 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol:
4-bromine o-phenylenediamine, 5-bromosalicylaldehyde and sodium pyrosulfite are dissolved in N, N-dimethyl methyl with the mole ratio of 1:1:1
In amide (DMF) solvent, heating reflux reaction 20～30 hours, pour into after being cooled to room temperature in frozen water, extract with ether, washing
Rear anhydrous sodium sulfate is dried, and rotary evaporation removes solvent, and solid crude product ethyl acetate and normal hexane are eluent, silicagel column
The layer isolated bromo-2-of beige solid 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol.
(2) preparation of the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol:
Bromo-for 4-2-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol and NaH are dissolved in anhydrous and oxygen-free with the mole ratio of 1:1.5
In DMF solvent, then the 1-bromooctane anhydrous and oxygen-free DMF dissolving of 1.05 molar equivalents is added dropwise over, is 30-80 in temperature
Under C, stirring reaction was poured in saturated aqueous common salt, with chloroform extraction, the anhydrous MgSO of extract after 20～40 hours4It is dried,
Rotary evaporation removes solvent, with petroleum ether and ethyl acetate mixtures as eluent, and silica gel column chromatography isolated rice white
The bromo-2-of solid 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol.
(3) preparation of metal complex BP-Cd:
By the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol and 2-cyano group-3-(the 8-hydroxyl of 1:1 molar equivalent
Base quinoline-5-base) acrylic acid is dissolved in anhydrous tetrahydro furan, the most dropwise drips and be slowly added to Cd (CH3COO)2
2H2The methanol solution of O, by dilute NaOH solution regulation reaction system to faintly acid, heating reflux reaction 10～20 hours, filters also
Wash with absolute methanol and oxolane and be vacuum dried to obtain the coordination compound that claret solid is cadmium (BP-Cd).
(4) by bromo-for 2,6-bis-4,8-bis-(5-(2-ethylhexyl) thienyl-2-base)-benzo [1,2-b:4,5-b'] two
Thiophene (BDTT), the coordination compound (BP-Cd) of cadmium, double (triphenylphosphine) Nickel dichloride., zinc powder, triphenylphosphine and 2,2 '-bipyridyl with
The ratio of 1:1:1:5:2:0.095 is dissolved in dry DMF, stirred under nitrogen atmosphere backflow (90 C) 24～72 hours, filters
Rear filtrate is poured in substantial amounts of ethanol solution, is sufficiently stirred for standing, and separates out solid and filters, and with absolute ethanol washing, obtains
Claret-red solid, closes the polymer-metal complex dye sensitizing agent of Cd (II) for the benzimidizole derivatives with BDTT as donor
PBDTT-BP-Cd。
(5) the bromo-4,8-of 2,6-bis-bis-(5-(2-ethylhexyl) thiophene is replaced with 9,9-dioctyl-2,7-dibromo fluorenes (FL)
Base-2-base)-benzo [1,2-b:4,5-b'] two thiophene (BDTT), synthesize with the reaction method similar with (4) with fluorene derivative
Orange red polymer-metal complex dye sensitizing agent PFL-BP-Cd for electron donor.
One class closes the D-A '-π-A type polymer-metal complex of Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
Purposes: in DSSC, be used as dye sensitizing agent.
The main advantage of invention is: the D-A ' of class conjunction Cd containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives (II)-
π-A type polymer-metal complex, by organometallic complex polymerization, to expand the big π system of complex molecule, improves it and inhales
Optical property and carrier transport ability；Study and replace noble ruthenium synthesized polymer metal complex with common B metal cadmium (II)
Dyestuff, will be substantially reduced sensitization solar battery cost and resource limit, and improve its photovoltaic performance.
Accompanying drawing explanation
The nucleus magnetic hydrogen spectrum of Fig. 1 embodiment of the present invention synthesis bromo-2-of 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol
(1HNMR) (400MHz, DMSO-d6, TMS)；
The nucleus magnetic hydrogen spectrum of Fig. 2 embodiment of the present invention synthesis bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol
(1HNMR) (400MHz, CDCl3, TMS)；
Infrared spectrum (the IR) (KBr of compound BP-Cd, PBDTT-BP-Cd and PFL-BP-Cd of the synthesis of Fig. 3 embodiment of the present invention
Crystal tabletting, 4000 ~ 400 cm-1)；
Thermogravimetric analysis (TGA) curve of compound PBDTT-BP-Cd and PFL-BP-Cd of Fig. 4 embodiment of the present invention synthesis；
The ultraviolet-visible light (UV-vis) of compound PBDTT-BP-Cd and PFL-BP-Cd of Fig. 5 embodiment of the present invention synthesis is inhaled
Receive spectrum；
The DSSC electric current of compound PBDTT-BP-Cd and PFL-BP-Cd of Fig. 6 embodiment of the present invention synthesis
Density vs. voltage (J-V) curve；
Measure outside the DSSC of compound PBDTT-BP-Cd and PFL-BP-Cd of Fig. 7 embodiment of the present invention synthesis
Sub-efficiency (IPCE) curve.
Detailed description of the invention
The reaction mechanism of the compound of the present invention is:
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1:
A kind of D-A-π-A type topology convergence metal complex closing Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
PBDTT-BP-Cd。
One is spread out using benzo two thiophene derivant (BDTT) as electron donor (D), 2-(2 '-hydroxy phenyl) benzimidazole
Biological close Cd (II) coordination compound be auxiliary electron acceptor (A '), the degree of polymerization be the polymerization gold of the D-A '-π-A type of x=10, y=10
Metal complex (PBDTT-BP-Cd), its molecular structural formula such as formula II:
Formula II.
The preparation implementation of above-mentioned polymer-metal complex PBDTT-BP-Cd.
A. the preparation of the bromo-2-of 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol: in 100 mL single port reaction bulbs, adds
4-bromine o-phenylenediamine 0.1870 g (1 mmol), sodium pyrosulfite 0.1909 g (1 mmol), 5-bromosalicylaldehyde 0.2010 g
(1 mmol), and dissolve with 50 mL DMFs (DMF), mixture is heated to reflux 24 h, is cooled to room temperature
After, reactant mixture to be poured in frozen water, products therefrom absolute ether (3 × 50 ml) extracts, and organic layer washes with water, anhydrous
Na2SO4It is dried.Remove solvent with Rotary Evaporators, remaining solid matter with ethyl acetate and normal hexane as developing solvent (1:5,
V:v), carry out column chromatography for separation purification and obtain target product, beige solid 0.2650 g(productivity 72%, characterize such as Fig. 1 institute
Show).FT-IR (KBr, 4000～400cm-1): 3460, 3357 (NH, OH), 3031 (CH, aromatic), 1446
(C=C), 1250 (C-O), 640 (C-Br). 1H-NMR (400 MHz, DMSO-d 6, δ): 13.40 (s, 1H),
12.88 (s, 1H), 8.34 (s, J = 13.7 Hz, 1H), 7.98 (s, 1H), 7.72-7.67 (d, 1H),
7.60-7.58 (d, J = 9.8 Hz, 1H), 7.50-7.49 (d, J = 11.8 Hz, 1H), 7.10-7.08 (d,J = 10.2 Hz, 1H). 13C-NMR (101 MHz, DMSO-d 6, δ): 157.38, 134.81, 129.32,
119.98, 115.11, 110.80. Anal. Calcd. for [C13H8Br2N2O] (%): C, 42.43; H, 2.19;
N, 7.61. Found (%): C, 42.40; H, 2.09; N, 7.72。
B. the preparation of the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol: at tri-mouthfuls of reaction bulbs of 50 mL
In, weigh the 0.3680 bromo-2-of g 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol (1 mmol), add 15 mL dry DMF molten
Solving, in reaction system, mixed solution is stirred at room temperature half an hour to be subsequently adding NaH (0.0360 g, 1.5 mmol)
Until escaping without gas.The 1-bromooctane (1.5 mmol) being dissolved in 5 mL dry DMF is added dropwise to reaction again
In system, after dripping, reactant mixture continues to react 24 h under temperature is 60 C under agitation.After reaction terminates,
Reactant liquor is poured in saturated aqueous common salt, and products therefrom chloroform extraction, organic layer washes with water, anhydrous MgSO4Dried
Night.Removing solvent with Rotary Evaporators, remaining solid silica gel column chromatography purifies (petroleum ether: ethyl acetate=10:1, work
For eluent), obtain beige solid target product 0.3892 g(productivity 79%, characterize as shown in Figure 2).FT-IR (KBr,
4000～400cm-1): 3428 (OH), 3077 (CH, aromatic), 2951 (CH3), 2880 (CH2). 1H-NMR
(400 MHz, CDCl3, δ): 10.68-10.64 (d, J = 14.5 Hz, 1H), 8.72 (s, 1H), 7.99 (s,
1H), 7.72-7.66 (m, 1H), 7.55-7.53 (d, J = 8.6 Hz, 1H), 7.44-7.36 (m, J =
17.8, 1H), 6.99-6.97 (d, J = 8.6 Hz, 1H), 4.26-4.25 (d, J = 5.9 Hz, 2H), 2.03
(s, 2H), 1.48-1.29 (t, J = 36.6 Hz, 10H), 0.93 (s, 3H). 13C-NMR (101 MHz,
CDCl3, δ): 155.35, 134.01, 132.50, 130.94, 128.86, 126.10, 119.27, 114.25,
114.24, 69.61, 65.61, 31.78, 30.60, 29.35, 29.26, 29.23, 29.13, 26.27, 22.66,
19.21, 14.10, 13.75. Anal. Calcd. for [C21H24Br2N2O] (%): C, 52.52; H, 5.04;
N, 5.83. Found (%): C, 52.54; H, 4.91; N, 5.91。
C. the preparation of metal complex BP-Cd: accurately weigh the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzene with electronic balance
And imidazoles-2-base) phenol (0.4802 g, 1 mmol), 2-cyano group-3-(8-hydroxyquinoline-5-base) acrylic acid (0.2402
G, 1 mmol) in three mouthfuls of reaction flasks, add anhydrous tetrahydro furan (15 mL) solvent and dissolve, under agitation,
Reactant mixture is made fully to dissolve.Cd (the CH being configured again3COO)22H2O's (0.2692 g, 1.01 mmol)
Absolute methanol (10 mL) solution is placed in constant pressure funnel, is dropwise added dropwise in reaction system, and dropping limit, limit is stirred.Treat
After it drips, by 1 mol L-1NaOH solution regulate the pH value of this reaction system to faintly acid.Then it is to slowly warm up to
Backflow, reacts 12 h.Being filtered by reaction mixture after being cooled to room temperature, filter cake absolute methanol and oxolane wash for several times,
Target product is finally vacuum dried to obtain claret solid 0.5401 g(productivity 65%, and Infrared Characterization is as shown in Figure 3).FT-IR
(KBr, 4000～400cm-1): 3432 (OH), 2942 (CH3), 2862 (CH2), 2216 (C≡N), 1680 (C=
O), 1615 (C=C), 1566 (C=N), 1105 (C-O-M), 497 (N-M). Anal. Calcd. for
[C34H30Br2N4O4Cd] (%): C, 49.15; H, 3.64; N, 6.74. Found (%): C, 49.13; H,
3.59; N, 6.77。
D. in 25 mL single port reaction bulbs, add the bromo-4,8-of monomer 2,6-bis-bis-(5-(2-ethylhexyl) thienyl-2-
Base)-benzo [1,2-b:4,5-b'] two thiophene (BDTT, 0.2947 g, 0.4 mmol), metal complex BP-Cd
(0.3323 g, 0.4 mmol), double (triphenylphosphine) Nickel dichloride. (0.2624 g, 0.4 mmol), zinc powder (0.1308 g, 2
Mmol), triphenylphosphine (0.2098 g, 0.8 mmol) and a small amount of 2,2 '-bipyridyl (0.0059 g, 0.038 mmol),
Add 15mL dry DMF solvent to dissolve.In reaction mixture, it is passed through nitrogen continuously three times, more gradually rises
Warm to 90 C, back flow reaction 48 h.After terminating Deng reaction, reaction mixture is cooled to room temperature, filters, then filtrate is poured into
In substantial amounts of ethanol solution, stirring, then stand, separate out a large amount of solid, filter, absolute ethanol washing used again by filter cake
For several times.After vacuum drying burgundy solid one containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives close Cd (II) D-A '-
π-A type topology convergence metal complex PBDTT-BP-Cd 0.2945 g(productivity 59%, Infrared Characterization is as shown in Figure 3).FT-IR
(KBr, 4000～400cm-1): 3422 (OH), 2935 (CH3), 2885 (CH2), 2845 (CH), 2204 (C≡
N), 1656 (C=O), 1606 (C=C), 1558 (C=N), 1096 (C-O-M), 490 (N-M). Anal. Calcd.
for (C68H70N4O4S4Cd)n (%): C, 65.44; H, 5.65; N, 4.49; S, 10.28. Found (%): C,
65.43; H, 5.54; N, 4.58; S, 10.33. M n=10.12 kg/mol, PDI=2.55。
Embodiment 2:
A kind of D-A '-π-A type topology convergence metal complex closing Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
PFL-BP-Cd。
A kind of using fluorene derivative (FL) as electron donor (D), close Cd containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives
(II) coordination compound is auxiliary electron acceptor (A '), degree of polymerization x=9, the D-A '-π-A type polymer-metal complex PFL-BP-of y=9
Cd, its molecular structural formula such as formula III:
Formula III.
The preparation method of above-mentioned polymer-metal complex PFL-BP-Cd.
Step A, B, C are consistent with the synthetic method of A, B, C in embodiment 1.
D. similar with step D in embodiment 1, only benzo two thiophene derivant (BDTT) is changed into 9,9-dioctyl-2,
7-dibromo fluorenes (FL), obtain Orange red solid one containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives close Cd (II) D-A '-
π-A type topology convergence metal complex PFL-BP-Cd 0.2289 g(productivity 54%, Infrared Characterization is as shown in Figure 3).FT-IR
(KBr, 4000～400cm-1): 3428 (OH), 2938 (CH3), 2856 (CH2), 2211 (C≡N), 1663 (C=
O), 1610 (C=C), 1563 (C=N), 1098 (C-O-M), 493 (N-M). Anal. Calcd. for
(C63H70N4O4Cd)n (%): C, 71.41; H, 6.66; N, 5.29. Found (%): C, 71.31; H, 6.57;
N, 5.38. M n=10.61 kg/mol, PDI=2.69。
Embodiment 3:
Measure the thermogravimetric curve (TGA) of polymer-metal complex dyestuff PBDTT-BP-Cd and PFL-BP-Cd respectively.Method:
Q50 thermogravimetric analyzer, N2Test with the programming rate of 25 DEG C/min under protection, test result such as Fig. 4.
Embodiment 4:
Control to measure by computer with Computer-programmed Keithley 2611 SourceMeter, Solar
Simulator (Oriel, 91160-1000 91192, Perccell Technologies) is light source (500-W Xe, AM
1.5 G), battery-active electrode effective area is 0.25cm2, measure respectively with polymer-metal complex PBDTT-BP-Cd and
PFL-BP-Cd is performance parameter and the photoelectric transformation efficiency of the DSSC of dye sensitizing agent, its battery current
Density vs. voltage (J-V) curve such as Fig. 6, battery external quantum efficiency (IPCE) curve such as Fig. 7.Table one be they photovoltaic performance and
Photoelectric transformation efficiency test result.
The photovoltaic performance parameter of table one polymeric dye sensitizer
Claims (3)
1. a class closes the polymer-metal complex dye sensitizing agent of Cd (II) containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives,
It is characterized in that, this compound has D-A '-π-A structure, its formula such as formula I:
Formula I.
The D-A '-π of a class the most according to claim 1 conjunction Cd containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives (II)-
The preparation method of A type polymer-metal complex (PBDTT-BP-Cd and PFL-BP-Cd):
(1) preparation of the bromo-2-of 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol:
4-bromine o-phenylenediamine, 5-bromosalicylaldehyde and sodium pyrosulfite are dissolved in N, N-dimethyl methyl with the mole ratio of 1:1:1
In amide (DMF) solvent, heating reflux reaction 20～30 hours, pour into after being cooled to room temperature in frozen water, extract with ether, washing
Rear anhydrous sodium sulfate is dried, and rotary evaporation removes solvent, and solid crude product ethyl acetate and normal hexane are eluent, silicagel column
The layer isolated bromo-2-of beige solid 4-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol；
(2) preparation of the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol:
Bromo-for 4-2-(6-bromo-1H-benzimidazolyl-2 radicals-yl) phenol and NaH are dissolved in anhydrous and oxygen-free with the mole ratio of 1:1.5
In DMF solvent, then the 1-bromooctane anhydrous and oxygen-free DMF dissolving of 1.05 molar equivalents is added dropwise over, is 30-80 in temperature
Under C, stirring reaction was poured in saturated aqueous common salt, with chloroform extraction, the anhydrous MgSO of extract after 20～40 hours4It is dried,
Rotary evaporation removes solvent, with petroleum ether and ethyl acetate mixtures as eluent, and silica gel column chromatography isolated rice white
The bromo-2-of solid 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol；
(3) preparation of metal complex BP-Cd:
By the bromo-2-of 4-(6-bromo-1-octyl group-1H-benzimidazolyl-2 radicals-yl) phenol and 2-cyano group-3-(the 8-hydroxyl of 1:1 molar equivalent
Base quinoline-5-base) acrylic acid is dissolved in anhydrous tetrahydro furan, the most dropwise drips and be slowly added to Cd (CH3COO)2
2H2The methanol solution of O, by dilute NaOH solution regulation reaction system to faintly acid, heating reflux reaction 10～20 hours, filters also
Wash with absolute methanol and oxolane and be vacuum dried to obtain the coordination compound that claret solid is cadmium (BP-Cd)；
(4) by bromo-for 2,6-bis-4,8-bis-(5-(2-ethylhexyl) thienyl-2-base)-benzo [1,2-b:4,5-b'] two thiophene
(BDTT), the coordination compound (BP-Cd) of cadmium, double (triphenylphosphine) Nickel dichloride., zinc powder, triphenylphosphine and 2,2 '-bipyridyl is with 1:1:
The ratio of 1:5:2:0.095 is dissolved in dry DMF, stirred under nitrogen atmosphere backflow (90 C) 24～72 hours, filters after filtration
Liquid is poured in substantial amounts of ethanol solution, is sufficiently stirred for standing, and separates out solid and filters, and with absolute ethanol washing, obtains claret-red
Solid, closes the polymer-metal complex dye sensitizing agent PBDTT-of Cd (II) for the benzimidizole derivatives with BDTT as donor
BP-Cd；
(5) the bromo-4,8-of 2,6-bis-bis-(5-(2-ethylhexyl) thienyl-2-is replaced with 9,9-dioctyl-2,7-dibromo fluorenes (FL)
Base)-benzo [1,2-b:4,5-b'] two thiophene (BDTT), synthesize with fluorene derivative as electricity with the reaction method similar with (4)
The orange red polymer-metal complex dye sensitizing agent PFL-BP-Cd of sub-donor.
The D-A '-π of a class the most according to claim 1 conjunction Cd containing 2-(2 '-hydroxy phenyl) benzimidizole derivatives (II)-
The purposes of A type polymer-metal complex PBDTT-BP-Cd and PFL-BP-Cd, is used as dyestuff in DSSC
Sensitizer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750194A (en) * | 2016-12-20 | 2017-05-31 | 湘潭大学 | One class benzimidazole derivative containing Phen closes polymer-metal complex of Cd (II) and its production and use |
| CN108084450A (en) * | 2017-12-22 | 2018-05-29 | 湘潭大学 | A kind of oligometric comples that cadmium is closed containing vinyl phenyl and to Ethenylbenzene phenolic group methylene amine derivative and preparation method thereof and purposes |
| CN108084448A (en) * | 2017-11-30 | 2018-05-29 | 湘潭大学 | One kind -1,2- of dimethyl containing 4,5- phenylenediamine derivatives close cadmium oligometric comples and preparation method and purposes |
| CN110606938A (en) * | 2018-06-14 | 2019-12-24 | 湘潭大学 | Polymeric complex containing 4-vinylpyridine cadmium and preparation method and application thereof |
| CN112209951A (en) * | 2019-07-12 | 2021-01-12 | 湘潭大学 | Benzimidazole derivative and 8-hydroxyquinoline derivative cadmium complex dye sensitizer and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084544A1 (en) * | 2007-12-27 | 2009-07-09 | Idemitsu Kosan Co., Ltd. | Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same |
| CN102471269A (en) * | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent element containing same |
| CN103540157A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof |
| CN103539804A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Phenothiazine-containing polymerization metal complex as well as preparation method and application thereof |
| EP2700641A1 (en) * | 2012-08-22 | 2014-02-26 | Solvay SA | Azulenocyanine analogue compounds comprising anchoring group, method of making the same, and their use as dye for dye-sensitized solar cells |
| KR20150133097A (en) * | 2014-05-19 | 2015-11-27 | (주)피엔에이치테크 | An electroluminescent compound and an electroluminescent device comprising the same |
| CN105722946A (en) * | 2013-09-30 | 2016-06-29 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting element using same |
-
2016
- 2016-07-01 CN CN201610503672.3A patent/CN106189363B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009084544A1 (en) * | 2007-12-27 | 2009-07-09 | Idemitsu Kosan Co., Ltd. | Nitrogen-containing heterocyclic derivative and organic electroluminescent device using the same |
| CN102471269A (en) * | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent element containing same |
| EP2700641A1 (en) * | 2012-08-22 | 2014-02-26 | Solvay SA | Azulenocyanine analogue compounds comprising anchoring group, method of making the same, and their use as dye for dye-sensitized solar cells |
| CN105722946A (en) * | 2013-09-30 | 2016-06-29 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting element using same |
| CN103540157A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Polymeric metal-complex functional dye containing 2-(2'-pyridyl)benzimidazole D-pi-A type structure and preparation method thereof |
| CN103539804A (en) * | 2013-10-31 | 2014-01-29 | 湘潭大学 | Phenothiazine-containing polymerization metal complex as well as preparation method and application thereof |
| KR20150133097A (en) * | 2014-05-19 | 2015-11-27 | (주)피엔에이치테크 | An electroluminescent compound and an electroluminescent device comprising the same |
Non-Patent Citations (1)
| Title |
|---|
| JIAOMEI HU: "Novel D–p–A dye sensitizers of polymeric metal complexes based on Cd(II) with salicylaldehyde and diaminomaleonitrile: synthesis, characterization,and photovoltaic performance for dye-sensitized solar cells", 《RES CHEM INTERMED》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750194A (en) * | 2016-12-20 | 2017-05-31 | 湘潭大学 | One class benzimidazole derivative containing Phen closes polymer-metal complex of Cd (II) and its production and use |
| CN106750194B (en) * | 2016-12-20 | 2020-05-22 | 湘潭大学 | Polymeric metal complex containing phenanthroline imidazole derivative and Cd (II), and preparation method and application thereof |
| CN108084448A (en) * | 2017-11-30 | 2018-05-29 | 湘潭大学 | One kind -1,2- of dimethyl containing 4,5- phenylenediamine derivatives close cadmium oligometric comples and preparation method and purposes |
| CN108084450A (en) * | 2017-12-22 | 2018-05-29 | 湘潭大学 | A kind of oligometric comples that cadmium is closed containing vinyl phenyl and to Ethenylbenzene phenolic group methylene amine derivative and preparation method thereof and purposes |
| CN108084450B (en) * | 2017-12-22 | 2021-05-07 | 湘潭大学 | Polymerization complex containing vinylphenyl and p-vinylphenol methylamine derivative cadmium and preparation method and application thereof |
| CN110606938A (en) * | 2018-06-14 | 2019-12-24 | 湘潭大学 | Polymeric complex containing 4-vinylpyridine cadmium and preparation method and application thereof |
| CN110606938B (en) * | 2018-06-14 | 2021-11-09 | 湘潭大学 | Polymeric complex containing 4-vinylpyridine cadmium and preparation method and application thereof |
| CN112209951A (en) * | 2019-07-12 | 2021-01-12 | 湘潭大学 | Benzimidazole derivative and 8-hydroxyquinoline derivative cadmium complex dye sensitizer and preparation method and application thereof |
| CN112209951B (en) * | 2019-07-12 | 2023-05-09 | 湘潭大学 | Dye sensitizer of benzimidazole derivative and 8-hydroxyquinoline derivative cadmium complex, and preparation method and application thereof |
| CN114196035A (en) * | 2021-12-17 | 2022-03-18 | 湘潭大学 | Four polymerization complexes using phenanthroline derivative as ligand, preparation method and application thereof |
| CN114196035B (en) * | 2021-12-17 | 2022-12-09 | 湘潭大学 | Four polymerization complexes using phenanthroline derivative as ligand, preparation method and application thereof |
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