WO2011091607A1 - 含芴卟啉-蒽共聚物、其制备方法和应用 - Google Patents
含芴卟啉-蒽共聚物、其制备方法和应用 Download PDFInfo
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- WO2011091607A1 WO2011091607A1 PCT/CN2010/070435 CN2010070435W WO2011091607A1 WO 2011091607 A1 WO2011091607 A1 WO 2011091607A1 CN 2010070435 W CN2010070435 W CN 2010070435W WO 2011091607 A1 WO2011091607 A1 WO 2011091607A1
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- WIPO (PCT)
- Prior art keywords
- porphyrin
- organic
- catalyst
- solvent
- copolymer
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 230000005669 field effect Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims abstract description 5
- 150000004032 porphyrins Chemical class 0.000 claims description 54
- 229910052707 ruthenium Inorganic materials 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- -1 fluorenyl porphyrin compound Chemical class 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002954 polymerization reaction product Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- 210000004027 cell Anatomy 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LQQKFGSPUYTIRB-UHFFFAOYSA-N 9,9-dihexylfluorene Chemical compound C1=CC=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 LQQKFGSPUYTIRB-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 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 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RPHBLSKZSDQVRO-UHFFFAOYSA-N C(CCCCCCCCC)C1(OBOC1(CCCCCCCCCC)CCCCCCCCCC)CCCCCCCCCC Chemical compound C(CCCCCCCCC)C1(OBOC1(CCCCCCCCCC)CCCCCCCCCC)CCCCCCCCCC RPHBLSKZSDQVRO-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C(C=C1)N=C1C(Br)=C(C=C1)NC1=C(C(C=C1)NC1=C(c1ccc(C)[n]1)Br*)[C@]1C=C(C(*)(*)c2c3cccc2)C3=CC1)C1=C(C=C)c2ccccc2C1(*)* Chemical compound CC(C(C=C1)N=C1C(Br)=C(C=C1)NC1=C(C(C=C1)NC1=C(c1ccc(C)[n]1)Br*)[C@]1C=C(C(*)(*)c2c3cccc2)C3=CC1)C1=C(C=C)c2ccccc2C1(*)* 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- IXADHCVQNVXURI-UHFFFAOYSA-N 1,1-dichlorodecane Chemical compound CCCCCCCCCC(Cl)Cl IXADHCVQNVXURI-UHFFFAOYSA-N 0.000 description 1
- YEYQUBZGSWAPGE-UHFFFAOYSA-N 1,2-di(nonyl)benzene Chemical compound CCCCCCCCCC1=CC=CC=C1CCCCCCCCC YEYQUBZGSWAPGE-UHFFFAOYSA-N 0.000 description 1
- ZPRQXVPYQGBZON-UHFFFAOYSA-N 2-bromo-1h-indole Chemical compound C1=CC=C2NC(Br)=CC2=C1 ZPRQXVPYQGBZON-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RSNPEOGYTFIJBE-UHFFFAOYSA-N C(C)(C)OB1OC(C(O1)(CCCCCCCCCC)CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC Chemical compound C(C)(C)OB1OC(C(O1)(CCCCCCCCCC)CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC RSNPEOGYTFIJBE-UHFFFAOYSA-N 0.000 description 1
- ZLXSWNVYGSZXOP-UHFFFAOYSA-N CC1(C)OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3c2cccc3)OC1(C)C Chemical compound CC1(C)OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3c2cccc3)OC1(C)C ZLXSWNVYGSZXOP-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- DXVWRJRZCMCNEU-UHFFFAOYSA-N dimercaptoamine Chemical compound SNS DXVWRJRZCMCNEU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WABAEEDHTRIFPM-UHFFFAOYSA-N hydroxy-sulfanyl-sulfanylidene-$l^{4}-sulfane Chemical compound SS(S)=O WABAEEDHTRIFPM-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- FTIMWVSQXCWTAW-UHFFFAOYSA-N ruthenium Chemical compound [Ru].[Ru] FTIMWVSQXCWTAW-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ZYSDERHSJJEJDS-UHFFFAOYSA-M tetrakis-decylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC ZYSDERHSJJEJDS-UHFFFAOYSA-M 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- 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
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Definitions
- the present invention relates to the field of organic materials, and in particular to a porphyrin-containing copolymer, a preparation method thereof and an application thereof.
- Organic solar cells are a new type of solar cells. Compared with inorganic semiconductor materials, which are limited in source, expensive, toxic, complicated in preparation process and high in cost, they have some advantages that inorganic solar cells cannot match, such as a wide range of materials. Structure diversity and controllability, low cost, safety and environmental protection, production process, light weight, large-area flexible preparation, etc., can be widely used in various fields such as construction, lighting and power generation, with important development and Application prospects.
- the photoelectric conversion efficiency of organic solar cells is still much lower than that of inorganic solar cells. Therefore, the development of new organic materials is of great significance for improving the efficiency of organic solar cells and other semiconductor devices or optoelectronic devices.
- a porphyrin-ruthenium-containing copolymer having a wide spectral response and good stability, and a preparation method of a porphyrin-ruthenium-containing copolymer having a simple synthesis route and low cost are provided.
- Embodiments of the present invention also provide the use of the above porphyrin-containing ruthenium copolymer in the manufacture of a solar cell device, an organic field effect transistor, an organic electroluminescent device, an organic optical memory device, an organic nonlinear material or an organic laser device.
- a porphyrin-containing ruthenium copolymer comprising the polymer represented by the following structural formula (1):
- RR 2 , R 3 , and R 4 are the same or different ( ⁇ -( 16 alkyl; n is an integer between 1 and 100).
- a method for preparing a porphyrin-containing ruthenium copolymer comprising the steps of:
- R 2 , R 3 , and R 4 are the same or different alkyl groups of C r C 16 ;
- the compounds VIII, B, and C are subjected to a polycondensation oxidation reaction to form a fluorenyl porphyrin compound;
- a thiol porphyrin compound is subjected to a bromination substitution reaction to produce a dibromo-substituted fluorenyl porphyrin compound;
- the dibromo-substituted indenyl porphyrin compound is subjected to Suzuki polymerization with the compound D in the presence of a catalyst, a solvent and an alkaline solution to obtain a polymer represented by the following structural formula (1):
- n in the structural formula (1) is an integer between 1 and 100.
- the ruthenium or its derivative contained has excellent photostability and thermal stability, and has an easily modified structure, which can be introduced by introducing a heterocyclic ring, a polyaromatic ring or a heterocyclic ring.
- the ring molecules increase the density of the skeletal electron cloud of the porphyrin-ruthenium-containing copolymer, so that the band gap of the copolymer is narrowed.
- the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reactions, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
- the ruthenium in the copolymer also has good stability and good film formability, and has good carrier transport properties, and has high hole mobility, thereby improving the porphyrin-containing copolymer.
- the carrier transport characteristics improve hole mobility.
- Figure 1 is a schematic view showing the structural formula of a porphyrin-containing ruthenium copolymer according to an embodiment of the present invention
- FIG. 2 is a flow chart showing a preparation method of a porphyrin-containing ruthenium copolymer according to an embodiment of the present invention
- Fig. 3 is a schematic view showing the structure of a porphyrin-ruthenium-containing copolymer-containing solar cell device according to an embodiment of the present invention.
- Fig. 4 is a view showing the structure of an organic electroluminescent device containing a porphyrin-ruthenium copolymer according to an embodiment of the present invention.
- Fig. 5 is a view showing the structure of an organic field effect transistor containing a porphyrin-ruthenium copolymer according to an embodiment of the present invention. detailed description
- a structural formula of a porphyrin-containing ruthenium copolymer according to an embodiment of the present invention which is a copolymer represented by the following structural formula (1):
- n is an integer between 1 and 100.
- the porphyrin-containing ruthenium copolymer has two identical alkyl-containing fluorene groups in each unit, that is, for example, R, and R 3 are the same C r C 16
- the alkyl group, R 2 and R 4 are the same -C ⁇ alkyl group, or in other words, 14 is the same -Cw alkyl group, and R 2 and R 3 are the same -C 16 alkyl group.
- R 2 , R 3 , and R 4 are the same ( ⁇ -(: 16 fluorenyl group.
- n) is preferably an integer of 5-50, more preferably 10-30.
- R t , R 2 , R 3 and R 4 are C 8 alkyl groups.
- the porphyrin-containing ruthenium copolymer includes ruthenium or a derivative thereof, a porphyrin structure, and a ruthenium structure.
- hydrazine or its derivatives have excellent photostability and thermal stability, and have a structure which is easy to modify, and can increase the porphyrin-containing copolymer by introducing a heterocyclic ring, a polyaromatic ring or an aromatic heterocyclic molecule.
- the density of the skeleton electron cloud narrows the band gap of the copolymer.
- the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reactions, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
- Bismuth also has good stability and good film formation, and has good carrier transport properties, and its hole mobility is high, so the carrier containing porphyrin-ruthenium copolymer can be improved. Transmission characteristics improve hole mobility.
- the above porphyrin-containing copolymer contains a plurality of thiophene rings, has a moderate band gap, a wide spectral response, a wavelength band of about 300-700 nm, substantially covers the visible light band, and has good thermal stability and Environmental stability, showing good photoelectric performance.
- Fluorene-containing porphyrins of the present embodiment - anthracene copolymer, RR 2, R 3, R4 is preferably an alkyl chain, for example C 6 alkyl chain or a C 6 above, by introducing an alkyl chain to improve the dissolution of the material Performance, which is conducive to film forming and expands its application range.
- the preparation method of the above-mentioned ruthenium-ruthenium-containing copolymer comprises the following steps:
- R 2 , R 3 , and R 4 are the same or different ( ⁇ ( ⁇ of the alkyl group;
- n in the structural formula (1) is an integer between 1 and 100.
- step S01 the compounds A, B, :, D can be directly obtained from the market or prepared by an existing synthesis method.
- the description is the same as the above description of the porphyrin-containing ruthenium-containing copolymer, and R 2 , R 3 and R 4 are the structural forms described above, and are not described herein again.
- R] are the same C r C 16 alkyl group, and R 2 and R 4 are the same dC 16 alkyl group, in which case the compounds A and B have the same structure.
- the compounds A, B, C, and D are prepared separately, as follows:
- the substitution reaction of 2-bromoindole with bromo alkane under a catalyst or a solvent to obtain 9,9-dialkyl-2-bromoindole is obtained.
- the catalyst is tetrabutylammonium bromide or benzyltriethylammonium chloride
- the solvent is toluene, disulfoxide, tetrahydrofuran or the like.
- the bromine is a bromine having an alkyl group of R and R 2 , respectively.
- the two reaction steps, i.e., steps i and ii were carried out separately using two bromines.
- the reaction route was as follows:
- reaction of bromination hydroformylation in an alkyllithium, dimercaptoamide and solvent system is as follows:
- the alkyl lithium is n-butyllithium and the solvent is tetrahydrofuran.
- the detailed preparation process can be found in the literature: Macromolecules, 2006, 39, 456.
- the condensation reaction is carried out in a system containing furfural, a catalyst and pyrrole to obtain a compound C, and the reaction equation is as follows:
- the catalyst of step iv may be trifluoroacetic acid or boron trifluoride dimethyloxy complex.
- pyrrole is both a solvent and a reactant.
- Detailed procedures for the preparation of dipyrrole, Compound C, can be found in the literature: Tetrahedron, 1994, 39, 1 1427.
- the specific implementation process is as follows: Under the protection of N 2 , add 9,10-dibromofluorene to a three-necked flask, inject 150 ml of tetrahydrofuran solvent, and slowly inject n-butyllithium with a syringe at -78 ° C. Stirring was continued for 2 hours, and 2-isopropoxy-4,4,5,5-tetradecyl-1,3,2-dioxaborolane was injected at -78 ° C, and stirred at room temperature overnight. . The reaction was quenched by the addition of aq. EtOAc. EtOAc (EtOAc) The liquid was subjected to silica gel column chromatography to give the product.
- the catalyst may be trifluoroacetic acid or the like, and the oxidizing agent may be dichlorodicyanobenzoquinone (DDQ) or the like, and is not limited thereto.
- the solvent may be dichlorosilane, tetrahydrofuran, or the like. Carbon chloride, chloroform or acetonitrile. Its reaction formula is as follows:
- the specific implementation process is as follows: Set up the anhydrous oxygen-free device, weigh the compounds A, B, C (for example, weighed in 1/1/2 of the molar ratio), dissolve in the dichlorosilane, pass nitrogen, add trifluoro Acetic acid, stirred, then add two molar equivalents of dichlorodicyanobenzoquinone (DDQ), continue to stir, then add triethylamine to quench the reaction, concentrate the solvent, filter, collect the filtrate and spin dry the solvent with dichloroguanidine Alkane on the silica gel column The extract was rinsed, the solvent was evaporated, and then crystallised from diethyl ether/methanol to product, i.
- DDQ dichlorodicyanobenzoquinone
- the solvent in the step S03 may be, but not limited to, chloroform or tetrahydrofuran, etc., and the specific implementation process is as follows: a mercaptoporphyrin compound (such as 5,15-bis(9,9-dialkylfluorene) porphyrin) is dissolved in chloroform. Add a small amount of pyridine, reduce the reaction to 0 ° C, add the appropriate amount of N-bromosuccinimide, stir, the mixture returned to room temperature, then continue to stir for several hours, add acetone to terminate the reaction, remove the solvent, with ether / decyl alcohol is recrystallized to give the product.
- the reaction is as follows:
- the catalyst in the step S04 may be an organic palladium catalyst in an amount of from 0.1 to 20% by mole based on the amount of the compound D.
- the organic palladium catalyst may be, for example but not limited to, Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 .
- the alkaline solution may be an inorganic alkali solution or an organic alkali solution, and the inorganic alkali solution may be an aqueous solution of an alkali metal hydroxide or an alkali metal carbonate, and may be, for example, but not limited to, a sodium hydroxide solution, a potassium hydroxide solution, or a sodium carbonate.
- the solution, the potassium carbonate solution or the like is preferably a sodium carbonate solution
- the organic solution may be an aqueous solution of an alkyl ammonium hydroxide, such as, but not limited to, tetradecyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl hydroxide.
- the above alkaline solution may be used in an amount of 5 to 20 times the molar amount of the compound D.
- the solvent is a weakly polar or polar aprotic organic solvent or a mixed solvent thereof, and may be, for example but not limited to, chloroform, dichlorodecane, ethylene glycol dioxime ether, dimercaptosulfoxide (DMSO), tetrahydrofuran (THF) And toluene, dinonylbenzene or the like, preferably toluene.
- the solvent is used in an amount sufficient to dissolve the respective reactants and sufficiently react.
- step S04 is as follows:
- step S04 The specific implementation process of the step S04 is as follows: 10 mmol of 1,4-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan) hydrazine is added to the round bottom flask. 1.0 mmol 5,15-dibromo-10,20-bis(9,9-dialkylfluorene) porphyrin, 0.01 mmol of tetrakis(triphenylphosphine)palladium, 3 ml of aqueous Na 2 C0 3 (2 mol/L And 20 ml of benzene solvent, vacuum deoxidation, and filled with nitrogen, the solution is heated to 50-120 ° C, the reaction is 12-80 hours.
- the product is then purified: the product of the reaction is poured into methanol, the precipitate is separated by filtration through a Buchner funnel, washed with dilute HC1, and the solid is washed with acetone in a Soxhlet extractor for 12-72 hours to remove The monomer and catalyst residue, the remaining polymer was dissolved in tetrahydrofuran and chloroform, which is the copolymer of this example.
- the n in the copolymer is preferably from 5 to 50, more preferably from 10 to 30.
- the desired degree of polymerization can be obtained by controlling the solvent, the reaction temperature, the reaction time, the amount of the reactant added, the type and amount of the catalyst.
- the synthesis routes of the three monomers of the compounds A, B and C are relatively simple and mature, and are basically one-step synthesis, thereby reducing the process flow and reducing the manufacturing cost.
- the bromination substitution reaction and the Suzuki polymerization reaction are a mature polymerization reaction with high yield, mild conditions, easy control, and easy introduction of an alkyl group to increase the solubility and molecular weight of the product to realize a spin-coatable polymer.
- the porphyrin-containing ruthenium copolymer of the present embodiment can be applied to various photovoltaic or semiconductor devices, for example, for solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical storage devices, organic nonlinearities. Materials and organic laser devices, etc.
- a solar cell device, an organic field effect transistor, and an organic electroluminescence device will be described as an example.
- Others such as organic optical storage devices, organic
- the linear material and the organic laser device are similar to the following, and are the optical storage materials, nonlinear materials, laser materials or semiconductor materials of the present embodiment using the porphyrin-containing copolymer.
- a solar cell device using the porphyrin-ruthenium-containing copolymer in the above embodiment which comprises a glass substrate 11, a transparent anode 12, an intermediate auxiliary layer 13, an active layer 14, and a cathode 15 which are sequentially laminated.
- the auxiliary layer 13 is made of polyethylene dioxythiophene: polystyrene-cross-acid composite material (abbreviated as PEDOT:PSS), the active layer 14 includes an electron donor material and an electron acceptor material, and the electron donor material adopts the above-mentioned ruthenium-containing material.
- the porphyrin-ruthenium copolymer, the electron acceptor material may be [6,6]phenyl-C 61 -butyrate butyrate (PCBM for short).
- the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ .
- the cathode 15 may be an aluminum electrode or a bimetal layer electrode such as Ca/Al or Ba/Al or the like.
- the glass base layer 11 can be used as a bottom layer, and when prepared, ITO glass is selected, and after ultrasonic cleaning, treated with oxygen-Plasma, an intermediate auxiliary layer 13 is coated on the ITO glass, and the porphyrin-onion copolymer and The electron acceptor material is applied to the intermediate auxiliary layer 13 by blending to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by a vacuum evaporation technique to obtain the above solar cell device.
- the transparent anode 12, the intermediate auxiliary layer 13, the active layer 14, the bimetal layer Ca, and the A1 layer have thicknesses of 160 nm, 40 nm, 150 nm, 20 nm, and 70 nm, respectively.
- the porphyrin-containing copolymer can more fully utilize light energy due to its wide spectral response range, thereby achieving higher photoelectric conversion efficiency and increasing the power generation capability of the solar cell device.
- the organic material can also reduce the quality of the solar cell device, and can be fabricated by spin coating techniques, etc., and is convenient for mass production.
- the device includes a glass base layer 21, a transparent anode 22, a light-emitting layer 23, a buffer layer 24, and a cathode 25 which are sequentially stacked.
- the transparent anode 22 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ / ⁇ .
- the light-emitting layer 23 contains the porphyrin-containing copolymer in the above examples.
- the buffer layer 24 may be LiF or the like, but is not limited thereto.
- the cathode 25 may be, but not limited to, metal A1 or Ba or the like, but is not limited thereto.
- the organic electroluminescent device structure is represented by: ITO/porphyrin-containing copolymer/LiF/Al.
- the layers can be formed by existing methods, and the porphyrin-containing copolymer can be formed on ITO by a spin coating technique.
- an organic field effect transistor using the porphyrin-ruthenium-containing copolymer in the above embodiment which comprises a substrate 31, an insulating layer 32, a modification layer 33, an organic semiconductor layer 34, and a layer which are sequentially stacked.
- the source electrode 35 and the drain electrode 36 on the organic semiconductor layer 34 may be, but not limited to, a highly doped silicon wafer (Si), and the insulating layer 32 may be, but not limited to, a micro-nano (eg, 450 nm) thick SiO 2 .
- the organic semiconductor layer 34 employs the above-described cerium-containing cerium-containing copolymer.
- Source electrode 35 and drain electrode 36 can be used without limitation.
- the modifying layer 33 can be, but is not limited to, octadecyltrichlorosilane.
- the substrate 31, the insulating layer 32, the modifying layer 33, and the source electrode 35 and the drain electrode 36 can be formed by a conventional method.
- the organic semiconductor layer 34 may be a spin coating of the porphyrin-containing ruthenium copolymer in the above embodiment on the insulating layer 32 modified by the modification layer 33.
- the preparation method of the porphyrin-containing ruthenium copolymer and its properties and the like are exemplified below by way of specific examples.
- the eight, B, C, and D in the following examples are directly prepared according to the above methods. Of course, in other embodiments, they may be directly purchased from the market, and are not limited thereto.
- 5,15-bis(9,9-dialkylfluorene)porphyrin is prepared, and 5,15-bis(9,9-dihexylfluorene)porphyrin is taken as an example, and the specific preparation process is as follows: Good anhydrous anaerobic device, weighed compounds A, B, C according to molar ratio 1: 1: 2, compounds A and B have the same structure, all are 9,9-dihexyl-2-yield, compound C is dipyrrole The decane was dissolved in dichloromethane, nitrogen was bubbled through for 30 minutes, trifluoroacetic acid was added by syringe, stirred at room temperature for 3 hours, and then two molar equivalents of dichlorodicyanobenzoquinone (DDQ) were added.
- DDQ dichlorodicyanobenzoquinone
- the third step the preparation of the porphyrin-containing copolymer, the structural formula of the porphyrin-containing copolymer of the present embodiment is:
- the specific formation process is as follows: 1,4-bis(4,4,5,5-tetradecyl-1,3,2-dioxaborolan) fluorene, 5,15-di is added to a round bottom flask. Bromo-10,20-bis(9,9-dihexylfluorene)porphyrin, tetrakis(triphenylphosphine)palladium, Na 2 CO 3 aqueous solution and toluene solvent, vacuum deoxidation and charging with nitrogen, the solution is first The mixture was refluxed for 48 hours under N 2 atmosphere, then poured into methanol, and the precipitate was separated by filtration using a Buchner funnel, and washed with dilute HC1, and the solid was washed with acetone in a Soxhlet extractor for 24 hours to remove the monomer and the catalyst residue. The remaining polymer was dissolved in tetrahydrofuran and chloroform in a yield of 32%.
- the ruthenium or its derivative contained has excellent photostability and thermal stability, and has a structure which is easy to repair and can be introduced by introducing a heterocyclic ring, a polyaromatic ring or The aromatic heterocyclic molecule increases the density of the skeletal electron cloud containing the porphyrin-ruthenium copolymer, so that the band gap of the copolymer is narrowed.
- the porphyrin structure enables the copolymer to have higher quantum efficiency of charge transfer and energy transfer reactions, good electron buffering and photoelectricity, good rigidity, good thermal stability and environmental stability.
- the ruthenium in the copolymer also has good stability and good film formation, and has good carrier transport properties. Since the hole mobility is high, the carrier transport characteristics of the porphyrin-ruthenium-containing copolymer can be improved, and the hole mobility can be improved.
- the above porphyrin-containing ruthenium copolymer is used in a solar cell device, an organic field effect transistor, an organic electroluminescence device, an organic optical memory device, an organic nonlinear material or an organic laser device, the photoelectric or semiconductor related performance can be improved. And can reduce the quality of the device and facilitate the preparation of large quantities.
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JP2012550292A JP5546070B2 (ja) | 2010-01-30 | 2010-01-30 | フルオレニルポルフィリン−アントラセンを含むコポリマー、その製造方法およびその応用 |
US13/575,684 US8598301B2 (en) | 2010-01-30 | 2010-01-30 | Copolymer containing fluorenylporphyrin-anthracene, preparation method and application thereof |
PCT/CN2010/070435 WO2011091607A1 (zh) | 2010-01-30 | 2010-01-30 | 含芴卟啉-蒽共聚物、其制备方法和应用 |
CN2010800481069A CN102686592B (zh) | 2010-01-30 | 2010-01-30 | 含芴卟啉-蒽共聚物、其制备方法和应用 |
EP10844385.4A EP2530084B1 (en) | 2010-01-30 | 2010-01-30 | Copolymer containing fluorenylporphyrin-anthracene, preparation method and use thereof |
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DE102009030847A1 (de) * | 2009-06-26 | 2010-12-30 | Merck Patent Gmbh | Polymere enthaltend substituierte Anthracenyleinheiten, Blends enthaltend diese Polymere sowie Vorrichtungen enthaltend diese Polymere oder Blends |
CN102712652B (zh) * | 2010-03-23 | 2014-03-19 | 海洋王照明科技股份有限公司 | 含芴卟啉-苯共聚物、其制备方法和应用 |
EP2562197B1 (en) * | 2010-04-23 | 2018-08-01 | Ocean's King Lighting Science & Technology Co., Ltd. | Copolymer comprising anthracene and benzoselenadiazole, preparing method and uses thereof |
JP5667693B2 (ja) * | 2010-05-18 | 2015-02-12 | ▲海▼洋王照明科技股▲ふん▼有限公司 | キノキサリン単位含有ポルフィリン共重合体及びその製造方法、並びにその応用 |
WO2011153680A1 (zh) * | 2010-06-07 | 2011-12-15 | 海洋王照明科技股份有限公司 | 含噻吩并噻二唑单元卟啉共聚物、其制备方法和应用 |
JP5538630B2 (ja) * | 2010-09-13 | 2014-07-02 | オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド | シラフルオレン金属ポルフィリン−ベンゼン有機半導体材料及びその調製方法並びに応用 |
CN103694246B (zh) * | 2013-12-23 | 2015-06-17 | 北京工业大学 | A3b型不对称卟啉类化合物的制备方法 |
CA3062176C (en) | 2017-05-04 | 2024-01-23 | Versa Power Systems Ltd. | Compact high temperature electrochemical cell stack architecture |
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US5371199B1 (en) * | 1992-08-14 | 1995-12-26 | Univ Pennsylvania | Substituted porphyrins porphyrin-containing polymers and synthetic methods therefor |
JP3150948B2 (ja) * | 1998-09-21 | 2001-03-26 | 科学技術振興事業団 | メソ位直結型ポルフィリンポリマーとその製造方法 |
JP4183402B2 (ja) * | 2001-07-18 | 2008-11-19 | 独立行政法人科学技術振興機構 | フラーレンを含む薄膜から成る光電変換素子用材料 |
JP4014960B2 (ja) * | 2002-07-31 | 2007-11-28 | 独立行政法人科学技術振興機構 | 分子ワイヤ及びその製造方法 |
KR100482276B1 (ko) | 2002-08-12 | 2005-04-13 | 한국과학기술연구원 | 피롤계 화합물, 그 중합체 및 이들을 이용한 el 소자 |
AU2003900404A0 (en) * | 2003-01-31 | 2003-02-13 | Massey University | Conducting polymers with porphyrin cross-linkers |
CN101817810A (zh) | 2003-10-31 | 2010-09-01 | 日产化学工业株式会社 | 酰基化合物的制造方法 |
JP4883898B2 (ja) * | 2004-11-18 | 2012-02-22 | パナソニック株式会社 | 電子デバイスおよびそれを用いた電子機器 |
FR2892723B1 (fr) | 2005-11-03 | 2009-04-24 | Biomerieux Sa | Nouveaux monomeres electropolymerisables, solubles en solution aqueuse, comportant une metalloporphyrine. |
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JP2013518151A (ja) | 2013-05-20 |
EP2530084A1 (en) | 2012-12-05 |
EP2530084B1 (en) | 2014-03-12 |
JP5546070B2 (ja) | 2014-07-09 |
EP2530084A4 (en) | 2013-06-12 |
US8598301B2 (en) | 2013-12-03 |
CN102686592A (zh) | 2012-09-19 |
CN102686592B (zh) | 2013-11-27 |
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