CN102504210B - 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 - Google Patents
主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 Download PDFInfo
- Publication number
- CN102504210B CN102504210B CN2011103190199A CN201110319019A CN102504210B CN 102504210 B CN102504210 B CN 102504210B CN 2011103190199 A CN2011103190199 A CN 2011103190199A CN 201110319019 A CN201110319019 A CN 201110319019A CN 102504210 B CN102504210 B CN 102504210B
- Authority
- CN
- China
- Prior art keywords
- aryl
- alkyl
- band gap
- narrow band
- conjugate polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 6
- 150000004696 coordination complex Chemical class 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 125000004429 atom Chemical group 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- -1 alkylthio-aryl Chemical group 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 4
- 125000001691 aryl alkyl amino group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000001769 aryl amino group Chemical group 0.000 claims description 4
- 125000005110 aryl thio group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052702 rhenium Chemical group 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical group [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Chemical group 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KZXODWQOXSIVDW-UHFFFAOYSA-N 3,8-dithiophen-2-yl-1,10-phenanthroline Chemical compound C1=CSC(C=2C=C3C(C4=NC=C(C=C4C=C3)C=3SC=CC=3)=NC=2)=C1 KZXODWQOXSIVDW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
- H10K85/30—Coordination compounds
- H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/37—Metal complexes
- C08G2261/374—Metal complexes of Os, Ir, Pt, Ru, Rh, Pd
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/414—Stille reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/91—Photovoltaic applications
-
- 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
- Y02E10/549—Organic PV 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- High Energy & Nuclear Physics (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明涉及一种主链中含有金属配合物的有机共轭高分子，其结构如式Ⅰ所示，其中，M代表过渡金属；
代表以N原子为配位原子的双齿配体，Ar代表含氮和/或硫的芳杂环；X-代表Cl-、Br-、I-、PF6 -、BF4 -、CF3SO3 -；n为10~100的整数。本发明有机共轭高分子，具有更高的光电转化效率，当应用于有机太阳能电池器件中时更有利于光电能量转化效率的提升。本发明有机共轭高分子可通过Suzuki或者Still偶联反应制备，反应条件温和可控，制备方法简单高效，适于大规模生产。
Description
技术领域
本发明属于有机光电材料领域，具体涉及一类主链中含有过渡金属配合物的窄带隙有机共轭高分子及其制备方法。
背景技术
有机聚合物太阳能电池由于质轻、易于加工、可大面积成膜、柔性、价格低廉及可实现卷对卷打印等优点，近十年来备受人们的关注而发展迅速。目前以窄带隙共轭高分子为主体材料的太阳能电池材料已经成为学术界和工业界的研究热点。一些大公司在有机薄膜太阳能电池的研发方面也取得了巨大的成功：美国的Solarmer Energy公司在2010年7月报道了光电转换效率为8.13%的有机聚合物薄膜太阳能电池器件；德国的Heliatek公司和美国的Konarka公司在2010年10月和11月分别报道了光电转换效率为8.3%的有机聚合物薄膜太阳能电池器件；最近日本的Mitsubishi Chemical公司报道了光电转换效率为9.2%的有机聚合物薄膜太阳能电池器件，已经十分接近有机太阳能电池工业化生产的效率门槛（10%的光电转换效率），有机太阳能电池的大规模应用指日可待（Service,R.F.Science2011,332,293.）。
目前报道的光电转换效率最高的太阳能电池器件所用的材料还集中于含噻吩、噻吩衍生物及类噻吩类基团单元的窄带系有机共轭高分子上。而研究发现，过渡金属配位化合物在可见光区有强烈吸收，因此可以预测，如果能够在有机太阳能电池器件中利用过渡金属对于提高太阳能电池的光电转化效率将有很大的帮助。
发明内容
本发明的目的是克服现有技术的不足，提供一种主链中含有过渡金属配合物的窄带隙有机共轭高分子，其具有更高的光电转化效率。
本发明的另一目的是提供上述主链中含有过渡金属配合物的窄带隙有机共轭高分子的制备方法。
本发明的第三个目的是将这种主链中含有过渡金属配合物的窄带隙有机共轭高分子应用到有机太阳能电池器件中。
为实现上述目的，本发明采取如下技术方案：
一种主链中含有过渡金属配合物的窄带隙有机共轭高分子，结构如式Ⅰ所示：
Ⅰ
其中，M代表过渡金属；代表以N原子为配位原子的双齿配体；Ar代表含氮和/或硫的芳杂环；X-代表Cl-、Br-、I-、PF6 -、BF4 -、CF3SO3 -；n为10～100的整数。
根据本发明，M为钌、铑或铼。
优选地，：
为以下结构：
其中，R为氢原子、卤素原子、烷基、烷氧基、烷硫基、烷基氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基乙炔基或者氰基。
进一步地，
为以下结构：
优选地，Ar为以下结构：
其中，R1为卤素原子、烷基、烷氧基、烷硫基、基烷氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基炔基或氰基。
进一步地，Ar为以下结构：
本发明含有过渡金属配合物的窄带隙有机共轭高分子，可以在Pd催化剂存在下，由含有两个氯、两个溴或两个碘的卤素基团的过渡金属配合物单体单元与含有两个硼酸基、硼酸酯基或者烷基锡基的芳杂环Ar单体单元通过Suzuki偶联反应或是Still偶联反应制备而得（Yin;Liebscher,J.Chemical Reviews2006,107,133-173.），且卤素基团优选为溴。
具体的反应方程式可用式Ⅱ表示：
Ⅱ。
上述的有机共轭高分子可应用于有机太阳能电池器件中。
由于以上技术方案的实施，本发明与现有技术相比具有如下优点：
本发明主链中含有过渡金属配合物的窄带隙有机共轭高分子，具有更高的光电转化效率，当应用于有机太阳能电池器件中时更有利于光电能量转化效率的提升；
本发明窄带隙有机共轭高分子通过Suzuki或者Still偶联反应制备，反应条件温和可控，制备方法简单高效，适于大规模生产。
附图说明
图1是实施例3中所制得的高分子polymer1在CHCl3溶液中的UV—vis吸收光谱图。
具体实施方式
下面结合具体的实施例对本发明做进一步详细的说明，但不限于这些实施例。
实施例1
配体3,8-二（2-溴噻吩）菲啰啉（化合物4）的合成，包括以下两步：
（1）、将5.00g3,8-二溴菲啰啉（化合物1），4.16g2-硼酸噻吩（化合物2），10.22gK2CO3，6.00g Bu4NBr（四丁基溴化铵）加入500.0mL三口烧瓶中，再加入100.0mLToluene（甲苯），75.0mL Ethanol（乙醇），50.0mL H2O，然后再向烧瓶中充N210min，再向烧瓶中加入1.71g Pd(PPh3)4[四（三苯基膦）钯]，用N2将烧瓶中的气体置换三次，最后在N2保护下加热至90℃搅拌反应59h。反应结束后旋转蒸发除去溶剂，再用CH2Cl2/H2O萃洗，浓缩有机相，然后以Al2O3为固定相，CH2Cl2/Et3N（三乙基胺）=50:1为流动相过柱分离提纯，得3,8-二噻吩基菲啰啉（化合物3）2.37g；
（2）、将1.40g步骤（1）制备所得的3,8-二噻吩基菲啰啉（化合物3）溶于20mL DMF和10mL CHCl3的混合溶剂中，然后在避光下向其中加入1.52g NBS（N-溴代丁二酰亚胺）的10mL DMF溶液，再在氩气保护下于50℃反应5h，反应结束后冷却至0℃后过滤，所得固体用水充分淋洗后干燥，得黄色固体产物1.84g[即化合物4，配体3,8-二（2-溴噻吩）菲啰啉]，收率：90.0%。化合物4的表征条件及结果如下：1H NMR(D6-DMSO，400MHz)，δ(ppm):9.36(d,J=2.0Hz,2H),8.61(d,J=2.0Hz,2H),7.99(s,2H),7.72(d,J=4.0Hz,2H),7.39(d,J=4.0Hz,2H)。
具体合成路线如下：
实施例2
含过渡金属钌的配合物单体7的合成：
将656.6mg化合物5,350.0mg化合物4加入100mL单口烧瓶中，再加入15.0mLHOCH2CH2OH，然后在N2保护下升温搅拌回流反应2h。反应结束后将反应液滴加到1.2gNH4PF6的15.0mL水溶液中（将化合物6转变为化合物7），有大量红色絮状沉淀生成，离心分离得深红色固体1.02g，再将所得深红色固体以CH2Cl2/CH3CH2OH=30:1为流动相，过硅胶柱分离提纯，得深红色固体化合物7纯品520.0mg，收率：45.8%。化合物7的表征条件及结果如下：1H NMR(D6-DMSO，400MHz),δ(ppm):9.02(d,J=2.0Hz,2H),8.84(s,2H),8.73(s,2H),8.31(s,2H),7.890(d,J=2.0Hz,2H),7.75(d,J=5.6Hz,2H),7.65(d,J=5.6Hz,2H),7.53(m,2H),7.46(d,J=4.0Hz,2H),7.38(d,J=4.0Hz,2H),7.22(m,2H),2.87(t,4H),2.72(t,4H),1.76(t,4H),1.62(t,4H),1.37-1.19(m,48H),0.82(m,12H)。
具体合成路线如下：
实施例3
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer1的合成：
将257.0mg单体7，116.0mg化合物8，8.0mg Pd(PPh3)4加入100mL三口烧瓶中，然后在N2保护下将3.0mL无水DMF(N,N-二甲基甲酰胺)、5.0mL无水甲苯加入烧瓶中，N2保护下升温搅拌回流反应40h。反应结束后将反应液滴加入约300mL CH3OH中，有大量固体析出，减压抽滤得红色固体，先将红色固体用硅藻土简单过滤以除去金属催化剂，然后再将红色固体放入索氏提取器中依次用正己烷、CH3OH、CHCl3为萃洗剂充分萃洗，最后取CHCl3萃洗液旋蒸除去溶剂得红色固体Polymer1约130mg。GPC：Mw（23×103g/mmol），PDI（1.18）。
具体合成路线如下：
实施例4
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer2的合成：
将257.0mg单体7，98.8mg化合物9，8.0mg Pd(PPh3)4加入100mL三口烧瓶中，然后在N2保护下将3.0mL无水DMF(N,N-二甲基甲酰胺)，5.0mL无水甲苯加入烧瓶中，N2保护下升温搅拌回流反应45h。反应结束后将反应液滴加入约300mL CH3OH中，有大量固体析出，减压抽滤，先将所得固体用硅藻土简单过滤以除去金属催化剂，然后再将固体放入索氏提取器中依次用正己烷、CH3OH、丙酮、四氢呋喃、CHCl3为萃洗剂充分萃洗，最后取CHCl3萃洗液旋蒸除去溶剂得固体产物Polymer2约210mg。GPC：Mw（56×103g/mmol），PDI（1.20）。
具体合成路线如下：
实施例5
主链中含金属钌配合物的窄带隙有机共轭高分子Polymer3的合成：
将257.0mg单体7，143.0mg化合物10，8.0mg Pd(PPh3)4加入100mL三口烧瓶中，然后在N2保护下将3.0mL无水DMF(N,N-二甲基甲酰胺)，5.0mL无水甲苯加入烧瓶中，N2保护下升温搅拌回流反应40h。反应结束后将反应液滴加入约300mL CH3OH中，有大量固体析出，减压抽滤，先将所得固体用硅藻土简单过滤以除去金属催化剂，然后再将固体放入索氏提取器中依次用正己烷、CH3OH、丙酮、四氢呋喃、CHCl3为萃洗剂充分萃洗，最后取CHCl3萃洗液旋蒸除去溶剂得固体产物Polymer3约230mg。GPC：Mw（36×103g/mmol），PDI（1.32）。
实施例6
对窄带隙有机共轭高分子Polymer1的电化学及光学性质进行测验：
电化学检测：
Polymer1的电化学性质是通过粘附在铂电极上的Polymer1的薄膜在无水无氧条件下经循环伏安法测定的，氧化起始电位Eox=0.78V,还原起始电位Ered=-1.15V,用二茂铁作基准物，将Eox、Ered带入公式EHOMO=-(Eox+4.80)(eV),ELUMO=-(Ered+4.80)(eV)得到Polymer1的EHOMO=5.58eV，ELUMO=-3.65eV,Eg=1.93eV。
光学检测：
对Polymer1的光谱性质进行检测，其UV—vis吸收光谱如图1所示。
由窄带隙有机共轭高分子Polymer1的HOMO—LUMO能级和UV—vis吸收光谱可知Polymer1在有机光伏领域有很好的应用前景。
以上对本发明做了详尽的描述，其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。
Claims (6)
1.一种主链中含有过渡金属配合物的窄带隙有机共轭高分子，其特征在于：所述窄带隙有机共轭高分子的结构如式Ⅰ所示：
Ⅰ
其中，M代表过渡金属；
代表以N原子为配位原子的双齿配体；Ar代表含氮和/或硫的芳杂环；X-代表Cl-、Br-、I-、PF6 -、BF4 -、CF3SO3 -；n为10～100的整数；
为以下结构：（1）（3）
Ar为以下结构：（31）
（34）
其中，R为氢原子、卤素原子、烷基、烷氧基、烷硫基、烷基氨基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基、芳基乙炔基或者氰基；
R1为卤素原子、烷基、烷氧基、烷硫基、芳基、芳氧基、芳硫基、芳基氨基、芳基烷基、芳基烷氧基、芳基烷硫基、芳基烷基氨基、酰基、酰氧基、酰胺基、亚氨基、烷基或芳基取代的甲硅烷基、烷基或芳基取代的甲硅烷氧基、烷基或芳基取代的甲硅烷硫基、烷基或芳基取代的甲硅烷基胺基、芳基烯基或氰基。
2.根据权利要求1所述的窄带隙有机共轭高分子，其特征在于：M为钌、铑或铼。
3.根据权利要求1所述的窄带隙有机共轭高分子，其特征在于：所述窄带隙有机共轭高分子的结构为如下结构式中的任一种：
4.权利要求1～3中任一项所述的窄带隙有机共轭高分子的制备方法，其特征在于：所述有窄带隙机共轭高分子通过Suzuki偶联反应或者Stille偶联反应制备而成。
5.根据权利要求4所述的制备方法，其特征在于：所述制备方法的反应方程式用式Ⅱ表示：
II.
6.权利要求1～3中任一项所述的窄带隙有机共轭高分子在有机太阳能电池器件中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103190199A CN102504210B (zh) | 2011-10-20 | 2011-10-20 | 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103190199A CN102504210B (zh) | 2011-10-20 | 2011-10-20 | 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504210A CN102504210A (zh) | 2012-06-20 |
| CN102504210B true CN102504210B (zh) | 2013-11-20 |
Family
ID=46216349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103190199A Expired - Fee Related CN102504210B (zh) | 2011-10-20 | 2011-10-20 | 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504210B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881060A (zh) * | 2012-12-24 | 2014-06-25 | 海洋王照明科技股份有限公司 | 一种萘并二噻吩基共聚物及其制备方法与聚合物太阳能电池 |
| CN108033982A (zh) * | 2017-12-25 | 2018-05-15 | 长春理工大学 | 一种聚集诱导磷光增强Re(I)配合物及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331586A (ja) * | 2003-05-08 | 2004-11-25 | Tokyo Institute Of Technology | １，１０−フェナントロリン誘導体、キレート配位子及び１，１０−フェナントロリン誘導体の製造方法 |
| CN101967164A (zh) * | 2010-09-10 | 2011-02-09 | 暨南大学 | 一种钌(ⅱ)配合物及其制备方法和在制备抗肿瘤药物中的应用 |
-
2011
- 2011-10-20 CN CN2011103190199A patent/CN102504210B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331586A (ja) * | 2003-05-08 | 2004-11-25 | Tokyo Institute Of Technology | １，１０−フェナントロリン誘導体、キレート配位子及び１，１０−フェナントロリン誘導体の製造方法 |
| CN101967164A (zh) * | 2010-09-10 | 2011-02-09 | 暨南大学 | 一种钌(ⅱ)配合物及其制备方法和在制备抗肿瘤药物中的应用 |
Non-Patent Citations (8)
| Title |
|---|
| Koiti Araki, Hiroaki Endo, Gou Masuda, Takuji Ogawa.Bridging nanogap electrodes by in situ electropolymerization of a bis (terthiophenylphenanthroline) ruthenium complex.《Chemistry-A European Journal》.2004,第10卷(第13期),全文. * |
| Koiti Araki, Hiroaki Endo, Gou Masuda, Takuji Ogawa.Bridging nanogap electrodes by in situ electropolymerization of a bis (terthiophenylphenanthroline) ruthenium complex.《Chemistry-A European Journal》.2004,第10卷(第13期),第3332页. * |
| Marek B. Majewski, Norma R. de Tacconi, Frederick M. MacDonn.Koiti Araki Dr.1,2,4, Hiroaki Endo1,2, Gou Masuda3, Takuji Ogawa.《Inorganic Chemistry》.2011,第50卷(第20期),全文. * |
| Wei Huang, Li Wang, Hirofumi Tanaka, Takuji Ogawa.Spectral, Structural, and Computational Studies of a New Family of Ruthenium(II) Complexes Containing Substituted 1,10-Phenanthroline Ligands and in situ Electropolymerization of a Phenanthrolineruthenium(II) Complex Bridging Nanogap Gold Electrodes.《European Journal of Inorganic Chemistry》.2009,第2009卷(第10期), * |
| Wei Huang, Li Wang, Hirofumi Tanaka, Takuji Ogawa.Spectral, Structural, and Computational Studies of a New Family of Ruthenium(II) Complexes Containing Substituted 1,10-Phenanthroline Ligands and in situ Electropolymerization of a Phenanthrolineruthenium(II) Complex Bridging Nanogap Gold Electrodes.《European Journal of Inorganic Chemistry》.2009,第2009卷(第10期),全文. * |
| YuanYuan Lü, LiHua Gao, MeiJiao Han, KeZhi Wang.Synthesis and the Effect of a Peripheral N‐Arylcarbazole Moiety on theAcid‐Base and DNA Binding Properties of a Novel RuII Complex.《European Journal of Inorganic Chemistry》.2005,第2006卷(第2期),全文. * |
| 项睿.201110319019.9.《STN检索报告》.2011, * |
| 项睿.201110319019.9.《STN检索报告》.2012, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504210A (zh) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101407574B (zh) | 含二噻吩并吡咯的给体-受体型共轭聚合物及制法和应用 | |
| CN102388085A (zh) | 包含苯并三唑单元的π-共轭低带隙共聚物 | |
| CN104177378A (zh) | 四取代的苝二酰亚胺二聚体、其制备方法及其在有机光伏器件中的应用 | |
| CN106749428B (zh) | 一种含N-噻吩基苯二胺衍生物合Co(II)的聚合金属配合物及其制备方法与用途 | |
| CN103288848A (zh) | 苯并三噻吩类化合物及其制备方法和用途 | |
| CN104045657A (zh) | 五元杂环衍生物桥联的苝二酰亚胺二聚体、其制备方法及其在有机光伏器件中的应用 | |
| CN114196035B (zh) | 四种以邻菲罗啉衍生物为配体的聚合配合物及其制备方法与用途 | |
| CN106188506A (zh) | 一类含8‑羟基喹啉衍生物合Cu(II)的聚合金属配合物染料敏化剂及其制备方法 | |
| CN109796581B (zh) | 一种含有低聚乙二醇侧链结构的窄带共轭聚合物及其制备方法和应用 | |
| CN103483560A (zh) | 一种2,1,3-苯并噻二唑并二噻吩衍生溴代物与咔唑的共轭聚合物及其合成方法 | |
| Chen et al. | A Novel Thiophene Derivative‐based Conjugated Polymer for Polymer Solar Cells with High Open‐circuit Voltage | |
| CN107805254B (zh) | 一种卟啉小分子钙钛矿阴极缓冲层材料及其制备方法与应用 | |
| CN103168062A (zh) | 一种光伏聚合物材料、其制备方法和应用 | |
| CN110194778B (zh) | 一种多臂结构有机光伏材料及其制备方法与应用 | |
| CN102504210B (zh) | 主链中含有金属配合物的窄带隙有机共轭高分子及其制备方法 | |
| CN102329418B (zh) | 一种基于1,2,4,5-四嗪的共轭聚合物及用于制备太阳能电池 | |
| CN108084409B (zh) | 一种宽带隙有机半导体材料及其制备方法和应用 | |
| CN108192083B (zh) | 含三氟甲基的共轭聚合物及其制备方法和应用 | |
| CN109956955B (zh) | 基于苯并三（环戊二烯并双五元芳杂环）的星型d-a结构共轭分子及其制备方法和应用 | |
| CN103304568A (zh) | 三聚吲哚类化合物及其制备方法和用途 | |
| CN103265687A (zh) | 含有大体积支化烷氧基侧链的聚合物材料、制备方法及应用 | |
| CN110642870B (zh) | Nti单体及其制备方法、其聚合物pntb1及其制备方法和应用 | |
| CN113929880A (zh) | 一类酯基噻唑类宽带隙聚合物及其在光电器件中的应用 | |
| CN106221280A (zh) | 一种新型含bodipy类共轭单元有机染料敏化剂及其制备方法 | |
| CN114479019B (zh) | 一种三嗪类聚合物材料及其制备方法和在光电器件中的应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |