CN116120156A - Dibromosubstituted hexabenzocoronene monomer, hexabenzocoronene conjugated polymer and preparation thereof - Google Patents
Dibromosubstituted hexabenzocoronene monomer, hexabenzocoronene conjugated polymer and preparation thereof Download PDFInfo
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- CN116120156A CN116120156A CN202310137468.4A CN202310137468A CN116120156A CN 116120156 A CN116120156 A CN 116120156A CN 202310137468 A CN202310137468 A CN 202310137468A CN 116120156 A CN116120156 A CN 116120156A
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- hexabenzocoronene
- organic solvent
- monomer
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- -1 Dibromosubstituted hexabenzocoronene Chemical class 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 27
- QRRKXCPLJGPVHN-UHFFFAOYSA-N hexabenzocoronene Chemical compound C12C(C(=C34)C(=C56)C7=C89)=C%10C7=C7C%11=CC=CC7=C8C=CC=C9C5=CC=CC6=C3C=CC=C4C1=CC=CC2=C1C%10=C%11C=CC1 QRRKXCPLJGPVHN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 73
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 56
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000003960 organic solvent Substances 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 27
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 23
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical group ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 21
- 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 20
- 238000001816 cooling Methods 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000004440 column chromatography Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 229940126214 compound 3 Drugs 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229940125898 compound 5 Drugs 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 claims description 6
- CCRMAATUKBYMPA-UHFFFAOYSA-N trimethyltin Chemical group C[Sn](C)C.C[Sn](C)C CCRMAATUKBYMPA-UHFFFAOYSA-N 0.000 claims description 6
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 5
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical group ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 2
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 2
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 2
- 244000038561 Modiola caroliniana Species 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 238000010129 solution processing Methods 0.000 abstract description 5
- 238000004528 spin coating Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 12
- 239000000370 acceptor Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- LECSAEIDPHEMMM-UHFFFAOYSA-N 3,4-dibromotridecacyclo[34.6.6.02,7.08,41.09,14.015,40.016,21.022,39.023,28.029,38.030,35.037,42.043,48]octatetraconta-1,3,5,7,9,11,13,15(40),16,18,20,22(39),23,25,27,29(38),30,32,34,36,41,43,45,47-tetracosaene Chemical compound BrC1=C(C=2C(=C3C4=C(C5=C6C(=C7C8=C(C9=C%10C(=C%11C%12=C(C=2C2=C3C5=C7C9=C%112)C=CC=C%12)C=CC=C%10)C=CC=C8)C=CC=C6)C=CC=C4)C=C1)Br LECSAEIDPHEMMM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229920005603 alternating copolymer Polymers 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- XHJPOZDMDBETDO-UHFFFAOYSA-N hexabenzo[a,d,g,j,m,p]coronene Chemical class C1=CC=CC2=C(C3=C45)C6=CC=CC=C6C4=C(C=CC=C4)C4=C(C=4C6=CC=CC=4)C5=C4C6=C(C=CC=C5)C5=C(C=5C6=CC=CC=5)C4=C3C6=C21 XHJPOZDMDBETDO-UHFFFAOYSA-N 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- CRBREIOFEDVXGE-UHFFFAOYSA-N dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1 CRBREIOFEDVXGE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- COHOGNZHAUOXPA-UHFFFAOYSA-N trimethyl(phenyl)stannane Chemical group C[Sn](C)(C)C1=CC=CC=C1 COHOGNZHAUOXPA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- 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
- C08G61/124—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 nitrogen atom in the ring
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
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- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/122—Copolymers statistical
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- 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
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The invention relates to a dibromo-substituted hexabenzocoronene monomer, a hexabenzocoronene conjugated polymer and preparation thereof, wherein the conjugated polymer has a chemical structural formula as follows:
wherein R is C 1 –C 30 Alkyl or alkoxy of (a); x and y are integers between 0 and 100; n is an integer between 1 and 200; b is pi bridge unit; a is an electron acceptor unit. Compared with the prior art, the polymer has excellent thermal stability, solubility and film forming property, is more suitable for preparing film by solution processing spin-coating method, has more uniform and complete film, better quality and greatly simplifies the organic electronic devicePreparation of the pieces.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and relates to a dibromo-substituted hexabenzocoronene monomer, a hexabenzocoronene conjugated polymer and preparation thereof.
Background
Conjugated polymer (conjugated polymers) is composed of sp 2 The hybridized bond length alternate carbon atom chain is constructed, and is a polymer with pi conjugated framework. The conjugated polymer has the advantages of low cost, light weight, good film forming property, good flexibility, suitability for solution processing, easiness in manufacturing large-area devices and the like, and has wide application prospect in the field of organic electronics. At present, molecular design strategies for conjugated polymers mainly construct donor-acceptor alternating copolymers, various electron donor units and electron acceptor units can be introduced into a polymer framework through reasonable structural design, the functional characteristics of each unit can be kept, and the properties of optical absorption, electron energy level and the like of the conjugated polymers can be flexibly regulated, so that ideal performances such as high carrier transmission and light capturing capacity and the like are obtained. At present, materials based on donor-acceptor alternating copolymers have been well applied in organic electronics fields such as Organic Light Emitting Diodes (OLEDs), organic Solar Cells (OSCs), organic Field Effect Transistors (OFETs), etc. However, to further enhance the performance of these organic electronic devices, the development of high performance donor-acceptor alternating copolymers places high demands on the creative design and synthesis of new electron donors and electron acceptors.
The non-planar hexabenzocoronene molecule (c-HBC) is formed by fusing thirteen six-membered rings, has a highly conjugated biconcave structure, can be regarded as a nano graphene fragment, and has the properties of high carrier mobility, high conductivity, excellent optical transparency, mechanical property and the like similar to graphene. Side chain substituted and modified hexabenzocoronene derivative, which is greatlyThe solubility of the hexabenzocoronene derivative in an organic solvent is improved, so that organic electronic devices such as organic solar cells, organic thin film transistors and the like can be easily prepared by a solution processing mode. In 2013, nuckolls team had dodecyloxy modified hexabenzocoronene (12-c-HBC) as electron donor material, fullerene derivative PC 70 BM as an electron acceptor material, a bulk heterojunction solar cell (J.Am.chem.Soc.2013, 135,6, 2207-2212) with a photoelectric conversion efficiency of 2.41% was fabricated by solution processing. In 2021, the Showcase male team covalently linked hexabenzocoronene and a bulky aryl unit, and the prepared blended film of hexabenzocoronene non-fullerene acceptor material (HBC-4-PDI) and reg-PThE polymer donor material obtained a photoelectric conversion efficiency of 2.70% (see patent application No. 202111500902.8). In addition to the application prospect in the aspect of organic solar cells, hexabenzocoronene and derivatives thereof also show carrier mobility of 0.61cm in organic thin film transistors 2 V -1 S -1 Is excellent (J.org.chem.2019, 84, 8562-8570). Although research shows that the hexabenzocoronene derivative has high carrier mobility, the research on the molecule is still limited for more than ten years, and small molecule compounds based on the hexabenzocoronene are reported to be deficient in film forming quality, so that inconvenience is brought to the preparation of devices. Conjugated polymers based on hexabenzocoronene units have not been reported. It is still a difficult problem how to design and construct hexabenzocoronene conjugated polymer materials which have broad and strong spectral absorption, proper electron energy levels and excellent film forming performance.
Disclosure of Invention
The invention aims to provide a dibromo-substituted hexabenzocoronene monomer, a hexabenzocoronene conjugated polymer and preparation thereof.
The aim of the invention can be respectively realized by the following technical proposal:
one of the technical schemes of the invention provides a dibromo-substituted hexabenzocoronene monomer, which has the chemical structural formula as follows:
wherein R is C 1 –C 30 Alkyl or alkoxy of (a).
The second technical scheme of the invention provides a preparation method of a dibromo-substituted hexabenzocoronene monomer, which comprises the following steps:
(1) Dissolving phenol in an organic solvent A, adding alkali, adding bromododecane under inert gas, reacting, cooling to room temperature after the reaction is finished, separating liquid, and removing the solvent to obtain light yellow liquid; under the protection of inert gas, adding anhydrous aluminum chloride and the pale yellow liquid into an anhydrous solvent B under the ice water bath, adding 4-bromobenzoyl chloride, reacting, cooling after the reaction is finished, quenching with ice water, separating liquid, and recrystallizing to obtain 4-bromo-4' -dodecyloxy-benzophenone, namely a compound 2;
(2) Dissolving the compound 2 in an organic solvent C, adding a reducing agent under the protection of inert gas, reacting, cooling after the reaction is finished, recrystallizing to obtain a white solid, dissolving the white solid in the organic solvent D, adding an oxidizing agent, continuing the reaction, and filtering the obtained reaction product to obtain a mauve liquid, namely the compound 3;
(3) Adding the compound 4 into a solution containing the compound 3 under the protection of inert gas in the dark, reacting overnight at room temperature, removing the solvent after the reaction is finished to obtain green solid, dissolving the green solid into an organic solvent E, adding triphenylphosphine, continuing the reaction under the protection of inert gas, cooling after the reaction is finished, removing the solvent, and purifying by column chromatography to obtain 6- ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacenequinone, namely the compound 5;
(4) Dissolving a compound 5 in an organic solvent F, adding an oxidant, stirring at room temperature for reaction, filtering after the reaction is finished, separating liquid, removing the solvent, purifying by column chromatography to obtain an orange-yellow solid, dissolving in an organic solvent G, adding a Lawson reagent, reacting under the protection of inert gas, cooling to room temperature, and purifying by column chromatography to obtain a light green solid compound 6;
(5) Dissolving a compound 6 in an organic solvent H, adding a compound 3 under the protection of inert gas and in the condition of avoiding light, reacting at normal temperature, removing the solvent after the reaction is finished, dissolving the obtained product in an organic solvent I, adding triphenylphosphine, reacting under the protection of inert gas, cooling after the reaction is finished, removing the solvent, and purifying by column chromatography to obtain (6E, 13E) -6, 13-bis ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacene quinone, namely a compound 7;
(6) Dissolving the compound 7 in an organic solvent J, carrying out illumination reaction under the action of iodine and propylene oxide under the protection of inert gas, removing the solvent and iodine simple substance after the reaction is finished, and purifying by column chromatography to obtain a compound 8, namely the target product dibromo-substituted hexabenzocoronene monomer;
the chemical structural formula of the compound 4 is as follows:
further, compound 4 was synthesized according to literature, starting from phthalic dicarboxaldehyde, and proceeding 3-step synthesis. (ref: angew. Chem. Int. Ed.2005,44, 7390-7394).
In the step (1), the organic solvent A is acetonitrile or ethyl acetate, the base is potassium carbonate or sodium carbonate, the molar ratio of phenol to base to bromododecane is (1:1.2-2:1-1.1), the reaction temperature is 60-90 ℃, and the time is 12-24h. The anhydrous solvent B is dichloromethane, chlorobenzene, dichlorobenzene or trichlorobenzene, the molar ratio of anhydrous aluminum chloride to the compound 1 to the 4-bromobenzoyl chloride is about (1:1:1), the reaction temperature is 30-50 ℃, and the reaction time is 12-24h.
Further, in the step (2), the organic solvent C is ethanol or n-amyl alcohol, the organic solvent D is tetrahydrofuran, dichloromethane or toluene, the reducing agent is hydrazine hydrate, the oxidizing agent is manganese dioxide, the molar ratio of the compound 2 to the reducing agent to the oxidizing agent is 1:10-20:8-15, the reaction temperature is 80-120 ℃, the reaction time is 12-24h, and the continuous reaction is carried out for 1-2h under the conditions of ice water bath and light shielding.
In the step (3), the organic solvent E is toluene or chlorobenzene, the molar ratio of the compound 3 to the compound 4 to the triphenylphosphine is 1:1.2-1.5:1.2-1.5, the continuous reaction temperature is 90-120 ℃, and the reaction time is 12-48h.
In the step (4), the organic solvent F is formed by mixing acetone and methylene dichloride according to the volume ratio of 1-3:3, the organic solvent G is toluene or chlorobenzene, the oxidant is potassium permanganate, the molar ratio of the compound 5 to the oxidant to the Lawson reagent is 1:2-4:0.8-1.2, and the reaction temperature is 85-100 ℃ under the protection of inert gas for 1-3h.
In the step (5), the organic solvent H is tetrahydrofuran, dichloromethane or toluene, the organic solvent I is toluene or chlorobenzene, the molar ratio of the compound 6 to the compound 3 to the triphenylphosphine is 1:1.5-2:1.2-1.5, and the reaction temperature is 90-120 ℃ under the protection of inert gas for 12-24 hours.
Further, in the step (6), the organic solvent J is toluene, and the molar equivalent ratio of the iodine simple substance to the compound 7 is at least 10:1, the mol ratio of the epoxypropane to the compound 7 is 800-1100:1, the light reaction is carried out under a high-pressure mercury lamp or an ultraviolet lamp, the reaction temperature is controlled to be not more than 40 ℃ in the light reaction process, and the time is 4-24 hours.
Furthermore, the inert atmosphere adopted in the preparation process of each step is argon.
The third technical scheme of the invention provides a hexabenzocoronene conjugated polymer, which is prepared from the dibromo-substituted hexabenzocoronene monomer as the raw material, wherein the conjugated polymer has a chemical structural formula as follows:
wherein R is C 1 –C 30 Alkyl or alkoxy of (a); x and y are integers between 0 and 100; n is an integer between 1 and 200; b is pi bridge unit; a is an electron acceptor unit.
Still further, B is selected from any one of the following groups:
wherein X is O, S or Se; r is R 1 Is hydrogen, C 1 ～C 30 A linear or branched alkyl group of F, cl or CN.
Still further, a is selected from any one of the following groups:
wherein R is 2 Is C 1 ～C 30 Straight or branched alkyl of (a); x is O, S or Se.
The invention provides a preparation method of hexabenzocoronene conjugated polymer, under the protection of inert gas, a dibromo-substituted hexabenzocoronene monomer, a dibromo-substituted A monomer and a bis (trimethyltin) -substituted B monomer are dissolved in an organic solvent K, a catalyst is added for reaction, trimethyltin and bromobenzene are added for continuous reaction, after the reaction is finished, after methanol washing, soxhlet extraction is carried out, and after methanol recrystallization, a terpolymer is obtained, namely a target product;
further, the chemical structural general formula of the dibromo-substituted A monomer is Br-A-Br, and the specific structural formula is as follows:
wherein R is 2 Is C 1 ～C 30 Straight or branched alkyl of (a); x is O, S or Se.
Further, the chemical structural formula of the B monomer substituted by bis (trimethyltin) is (CH) 3 ) 3 Sn-B-Sn(CH 3 ) 3 The specific structural formula is as follows:
wherein X is O, S or Se; r is R 1 Is hydrogen, C 1 ～C 30 A linear or branched alkyl group of F, cl or CN.
Further, the organic solvent K used is chlorobenzene or toluene.
Further, the catalyst used was tris (dibenzylideneacetone) dipalladium (Pd 2 (dba 3 ) Tris (o-methylphenyl) phosphorus (P (o-tol) 3 ) Is prepared by compounding.
Further, the end capping agent is trimethyl (phenyl) tin and bromobenzene.
Further, the extractant used for Soxhlet extraction is methanol, acetone, n-hexane and chloroform in sequence.
Further, the molar ratio of dibromo-substituted hexabenzocoronene monomer, dibromo-substituted A monomer, bis (trimethyltin) -substituted B monomer, trimethyltin (phenyl) to bromobenzene is x:y:1:5-10:5-10, wherein x+y=1; the amounts of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphorus were 0.02eq and 0.08eq, respectively.
Further, the temperature of the reaction after adding the catalyst is 100-120 ℃ and the time is 24-72h.
Further, the temperature of the continuous reaction is 100-120 ℃ and the time is 24-48h.
Compared with the prior art, the invention has the following advantages:
(1) The dibromo-substituted hexabenzocoronene monomer is prepared for the first time, can be subjected to Stille coupling reaction with an organic compound containing trimethyltin, and can also be subjected to Suzuki coupling reaction with an organic compound containing boric acid or boric acid ester to obtain hexabenzocoronene conjugated small molecules or conjugated polymers.
(2) Compared with the prior reported hexabenzocoronene small molecular compound, the purification method is simple and efficient, the ultraviolet-visible light absorption spectrum is obviously widened from about 350nm to about 450nm to 350nm to 907nm (J.am. Chem. Soc.2013,135,6, 2207-2212), and the wider absorption spectrum shows that the hexabenzocoronene conjugated polymer is suitable for photoactive materials in organic electronic devices such as organic solar cells, organic light response field effect transistors, organic photodetectors and the like.
(3) The strategy of the present donor-acceptor ternary polymerization reduces the electrochemical Highest Occupied Molecular Orbital (HOMO) energy level from-5.21 eV to-5.40 eV (Sustainable Energy Fuels,2018,2,2154-2159) compared to the conventional donor-acceptor alternating copolymer P (DPP-TT). In organic field effect transistors, moderate reduction of HOMO energy levels can inhibit the doping of materials by oxygen in the air, thereby improving the stability of the device; in an organic solar cell, the lower the HOMO energy level of a polymer donor material, the larger the energy level difference between the polymer donor material and the Lowest Unoccupied Molecular Orbital (LUMO) energy level of a fullerene acceptor material can be generated, and more driving force is provided for exciton dissociation, so that the open-circuit voltage and the photoelectric conversion efficiency of a photovoltaic device are improved.
(4) Compared with hexabenzocoronene small molecular compounds, the polymer provided by the invention is more suitable for preparing a film by a solution processing spin-coating method, and the obtained film is more uniform, complete and better in quality, and greatly facilitates the preparation of an organic electronic device.
Drawings
FIG. 1 is a process scheme of example 1;
FIG. 2 shows the compound 2 produced 1 H-NMR chart;
FIG. 3 shows the compound 5 prepared 1 H-NMR chart;
FIG. 4 shows the compound 7 prepared 1 H-NMR chart;
FIG. 5 shows the compound 8 prepared 1 H-NMR chart;
FIG. 6 shows the PHBCTT-30% of the polymer of the invention 1 H-NMR chart;
FIG. 7 is a graph of thermogravimetric analysis of PHBCTT-30% of the polymer of the present invention;
FIG. 8 is a gel permeation chromatogram of the polymer PHBCTT-30% of the present invention;
FIG. 9 is a graph showing the ultraviolet-visible light absorption spectrum of the polymer PHBCTT-30% of the present invention;
FIG. 10 is a graph of electrochemical cyclic voltammetry of polymer PHBCTT-30% of the present invention;
FIG. 11 is an optical micrograph of (a) a polymer PHBCTT-30% film of the present invention and (b) a HBC small molecule compound film.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and reagents, materials, etc. used in the following examples are commercially available unless otherwise specified.
In addition, the 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (5-decyldodecyl) pyrrolo [3,4-C ] pyrrole-1, 4 (2 h,5 h) dione used, compound 9, was synthesized according to reference j.am.chem.soc.2021,143, 11679-11689.
Example 1:
a synthetic method of dibromo-substituted hexabenzocoronene monomer and hexabenzocoronene conjugated polymer is shown in FIG. 1, and comprises the following steps:
(1) Phenol (20 g,212.52 mmol) was dissolved in 300mL of acetonitrile, potassium carbonate (42 g,303.90mmol,1.43 eq) was added, and bromododecane (54 mL,225.32mmol,1.06 eq) was slowly added by syringe under argon protection and reacted at 80℃for 12h. After the reaction, cooling to room temperature, filtering, removing acetonitrile by vacuum rotary evaporation, adding 200mL of ethyl acetate and 100mL of saturated saline, separating liquid, removing trace water by using anhydrous sodium sulfate, and removing ethyl acetate by vacuum rotary evaporation to obtain light yellow liquid.
Anhydrous aluminum chloride (8.67 g,64.8 mmol) was weighed, dodecyloxybenzene (i.e., compound 1,17.06g,65 mmol) and 100mL of dehydrated and deoxygenated dichloromethane were added dropwise to a constant pressure dropping funnel, and the ice water bath was conducted for 10min. After 4-bromobenzoyl chloride (14.22 g,64.8 mmol) was dissolved in 50mL of water-scavenging dichloromethane, slowly added dropwise via a constant pressure dropping funnel. Slowly heating to 40 ℃, and reacting for 12 hours. After the reaction, the mixture was cooled to room temperature, poured into ice water and quenched. Separating liquid, removing most of solvent by vacuum rotary evaporation, adding methylene dichloride: methanol=1: 5 solvent 100mL, recrystallisation and drying in a vacuum oven (60 ℃ C.) for 12h gave 21.47g of pale pink squamous solid in 74.38% yield.
(2) 4-bromo-4' -dodecyloxy-benzophenone (i.e. compound 2,21.47g,48.2 mmol) was dissolved in 60mL of n-pentanol, hydrazine hydrate (41.2 g,823mmol,17 eq) was added under argon protection, heated to 120℃and reacted for 12h. After the reaction was completed, the reaction mixture was cooled to room temperature, recrystallized from methanol and dried to obtain 19.22g of a white solid with a yield of 86.8%.
The above white solid (9.5 g,20.68 mmol) was dissolved in 60mL of tetrahydrofuran, deoxygenated by water removal, and manganese dioxide (18 g,206.8mmol,10 eq) was added in three portions with an ice-water bath protected from light. After the reaction is finished, the light-shielding suction filtration is carried out, and the reaction is directly carried out in the next step.
(3) A tetrahydrofuran solution (18.27 mmol) of product 3 was added to product 4 (12.18 mmol) under protection from light at room temperature for 5h. And after the reaction is finished, removing the solvent by vacuum rotary evaporation to obtain a light green solid.
The pale green solid (13.31 mmol) was dissolved in 150mL of dehydrated and deoxygenated toluene, triphenylphosphine (5.21 g,19.86mmol,1.5 eq) was added, and the mixture was reacted at 105℃for 24h under inert gas. After the reaction is finished, cooling to room temperature, filtering, removing solvent toluene by vacuum rotary evaporation, purifying by column chromatography, and selecting petroleum ether as an eluent: dichloromethane = 4:1, 1.2g of a white solid (compound 5) was obtained in 17% yield.
(4) 6- ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacenequinone (i.e., compound 5,0.86g,1.21 mmol) was dissolved in dichloromethane: acetone=1: 2 to the solvent, potassium permanganate (0.57 g,3.63 mmol) was added and the reaction was carried out at room temperature for 2 hours. After the reaction is finished, adding excessive NaHSO 3 :Na 2 SO 3 Solution quenching residual potassium permanganate=2:1. Filtering, removing most of the solvent by vacuum rotary evaporation, adding 200mL of deionized water and 50mL of dichloromethane for separating, adding saturated salt water solution, removing trace water by anhydrous sodium sulfate, removing the solvent by vacuum rotary evaporation, separating by column chromatography, and selecting petroleum ether as eluent: dichloro-sMethane=4:1 to 1:1, to give a yellow solid.
The yellow solid from the previous step (1.4 g,1.94 mmol) was dissolved in 50mL toluene and L.complex reagent (1.18 g,2.91mol,1.5 eq) was added and reacted for 2h at 95℃under inert gas. Cooling to room temperature, separating by column chromatography, wherein the eluent is petroleum ether: dichloromethane=4:1 to give compound 6.
(5) A tetrahydrofuran solution of compound 3 (1.56 g,3.52mmol,2 eq) was added to compound 6 (1.3 g,1.76 mmol) under protection of argon at room temperature for 5h. After the reaction, tetrahydrofuran was removed by rotary evaporation under vacuum to give a green solid.
The green solid from the previous step (1.87 g,1.6 mmol) was dissolved in 60mL toluene and triphenylphosphine (0.51 g,1.92mmol,1.2 eq) was added and reacted for 24h at 105℃under argon. After the reaction is finished, the solvent is removed by vacuum rotary evaporation, column chromatography is carried out, and petroleum ether is selected as the leaching agent: dichloromethane=6:1 to give (6 e,13 e) -6, 13-bis ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacenequinone (compound 7) as a white solid 0.35g, 20% yield.
(6) To the inner layer of the photoreactor was added compound 7 (157 mg,0.14 mmol), followed by 320mL of toluene and propylene oxide (10 mL,142.9 mmol) and argon for 30 min. Elemental iodine (312 mg,1.23mmol,8 eq) was added and the outer layer of the photoreactor was cooled, and the entire photoreactor was immersed in a water-filled tank and then purged with argon for 30 minutes. And a 500W high-pressure mercury lamp is placed and irradiated for 4 hours. After the reaction is finished, removing the solvent toluene and iodine by vacuum rotary evaporation, separating by column chromatography, and selecting petroleum ether as a leaching agent: dichloromethane=6:1. After methanol recrystallization, drying for 4 hours at normal temperature in a vacuum drying oven, 130mg of dibromohexabenzocoronene (compound 8) is obtained, and the yield is 82.4%.
(7) 3, 6-bis (5-bromothiophen-2-yl) -2, 5-bis (5-decyldodecyl) pyrrolo [3,4-C ] pyrrole-1, 4 (2 h,5 h) dione (compound 9, 85.09mg,0.07 mmol), 2, 5-bis (trimethyltin) thiophene [3,2-b ] thiophene (46.58 mg,0.1 mmol) and dibromohexabenzocoronene (compound 8,33.81mg,0.03 mmol) were dissolved in 7mL chlorobenzene and argon was purged for 15 min. Tri (dibenzylideneacetone) dipalladium (1.83 mg,0.02mmol,0.02 eq) and tris (o-methylphenyl) phosphorus (2.43 mg,0.008mmol,0.08 eq) were added and argon was continuously passed through for 15 min. First at 110℃for 24h and then at 130℃for 24h. After cooling, trimethyltin (22 mg,0.09mmol,0.9 eq) was added and reacted at 110℃for 20h. Bromobenzene (15.7 mg,0.1mmol,1 eq) was added after cooling again and reacted at 110℃for 20h. After the reaction is finished, cooling, dripping into 200mL of methanol, carrying out suction filtration, and putting filter cakes into a Soxhlet extractor, wherein the following steps are adopted respectively: extracting with methanol at 110deg.C for 20 hr; extracting with acetone at 90deg.C for 20 hr; extracting with n-hexane at 90deg.C for 20 hr; extracting with chloroform at 90deg.C for 12 hr. Part of chloroform was removed, and the mixture was added dropwise to 200mL of methanol, followed by suction filtration and drying to give polymer 10 (100.5 mg) in a yield of 58.51%.
FIG. 2 shows the compound 2 produced 1 An H-NMR chart of the sample, 1 H NMR(400MHz,Chloroform-d)δ7.78(d,J＝8.3Hz,2H),7.62(s,4H),6.95(d,J＝8.3Hz,2H),4.04(t,J＝6.6Hz,2H),1.82(p,J＝6.9Hz,2H),1.47(p,J＝7.2Hz,2H),1.40–1.20(m,16H),0.88(t,J＝6.6Hz,3H)。
FIG. 3 shows the compound 5 prepared 1 An H-NMR chart of the sample, 1 H NMR(400MHz,Chloroform-d)δ7.74(d,J＝19.6Hz,4H),7.57(s,1H),7.50–7.45(m,3H),7.40–7.27(m,6H),7.23–7.19(m,4H),6.76–6.72(m,2H),4.31(s,2H),3.85(t,J＝6.6Hz,2H),1.71(p,J＝6.8Hz,2H),1.38(d,J＝8.4Hz,2H),1.26(d,J＝8.0Hz,16H),0.90–0.87(m,4H)。
FIG. 4 shows the compound 7 prepared 1 An H-NMR chart of the sample, 1 H NMR(400MHz,Chloroform-d)δ7.56(s,2H),7.48(s,2H),7.46–7.36(m,8H),7.32–7.27(m,9H),7.25–7.18(m,3H),6.80–6.76(m,4H),3.88(t,J＝6.6Hz,4H),1.77–1.68(m,4H),1.27(d,J＝10.8Hz,39H),0.90–0.87(m,6H)。
FIG. 5 shows the compound 8 prepared 1 An H-NMR chart of the sample, 1 H NMR(400MHz,Chloroform-d)δ9.37(dd,J＝6.3,2.0Hz,2H),9.34–9.30(m,2H),9.16(dd,J＝6.6,3.4Hz,2H),9.05(d,J＝2.3Hz,2H),9.03(d,J＝2.0Hz,2H),8.66(dd,J＝5.0,2.6Hz,2H),7.89–7.82(m,6H),7.47–7.44(m,2H),4.33(d,J＝7.7Hz,2H),4.21(t,J＝7.2Hz,2H),1.95(t,J＝7.4Hz,4H),1.39–1.24(m,36H),0.86(d,J＝6.9Hz,6H)。
FIG. 6 shows the PHBCTT-30% of the polymer of the invention 1 H-NMR chart.
FIG. 7 is a graph of thermogravimetric analysis of polymer PHBCTT-30% showing the polymerizationThermal decomposition temperature T of the compound with a thermal weight loss of 5% d Is 399.8 ℃, and has excellent thermal stability.
FIG. 8 is a gel permeation chromatogram of PHBCTT-30% of a polymer showing the number average molecular weight M of the polymer n 22.0kDa, weight average molecular weight M w 55.6kDa and a molecular weight distribution index PDI of 2.5.
FIG. 9 is an ultraviolet-visible light absorption spectrum of the polymer PHBCTT-30%, showing that the absorption peaks of the polymer are very weak at 726nm and 390nm and the aggregation absorption peak is about 800nm, showing that the intermolecular aggregation effect is weak.
FIG. 10 is an electrochemical cyclic voltammogram of polymer PHBCTT-30%, and the HOMO and LUMO energy levels of the polymer are respectively-5.397 eV and-3.532 eV calculated by oxidation and reduction curves, showing that the polymer has a lower HOMO energy level.
FIG. 11 is an optical microscopic image of (a) PHBCTT-30% film and (b) HBC small molecule compound film, where the film formed by the polymer is more compact and flat, and the small molecules have voids, indicating that the polymer has good film forming property.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A dibromo-substituted hexabenzocoronene monomer, which is characterized by the following chemical structural formula:
wherein R is C 1 –C 30 Alkyl or alkane of (2)An oxy group.
2. The method for preparing the dibromo-substituted hexabenzocoronene monomer according to claim 1, which comprises the following steps:
(1) Dissolving phenol in an organic solvent A, adding alkali, adding bromododecane under inert gas, reacting, cooling to room temperature after the reaction is finished, separating liquid, and removing the solvent to obtain light yellow liquid; under the protection of inert gas, adding anhydrous aluminum chloride and the pale yellow liquid into an anhydrous solvent B under the ice water bath, adding 4-bromobenzoyl chloride, reacting, cooling after the reaction is finished, quenching with ice water, separating liquid, and recrystallizing to obtain 4-bromo-4' -dodecyloxy-benzophenone, namely a compound 2;
(2) Dissolving the compound 2 in an organic solvent C, adding a reducing agent under the protection of inert gas, reacting, cooling after the reaction is finished, recrystallizing to obtain a white solid, dissolving the white solid in the organic solvent D, adding an oxidizing agent, continuing the reaction, and filtering the obtained reaction product to obtain a mauve liquid, namely the compound 3;
(3) Adding the compound 4 into a solution containing the compound 3 under the protection of inert gas in the dark, reacting overnight at room temperature, removing the solvent after the reaction is finished to obtain green solid, dissolving the green solid into an organic solvent E, adding triphenylphosphine, continuing the reaction under the protection of inert gas, cooling after the reaction is finished, removing the solvent, and purifying by column chromatography to obtain 6- ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacenequinone, namely the compound 5;
(4) Dissolving a compound 5 in an organic solvent F, adding an oxidant, stirring at room temperature for reaction, filtering after the reaction is finished, separating liquid, removing the solvent, purifying by column chromatography to obtain an orange-yellow solid, dissolving in an organic solvent G, adding a Lawson reagent, reacting under the protection of inert gas, cooling to room temperature, and purifying by column chromatography to obtain a light green solid compound 6;
(5) Dissolving a compound 6 in an organic solvent H, adding a compound 3 under the protection of inert gas and in the condition of avoiding light, reacting at normal temperature, removing the solvent after the reaction is finished, dissolving the obtained product in an organic solvent I, adding triphenylphosphine, reacting under the protection of inert gas, cooling after the reaction is finished, removing the solvent, and purifying by column chromatography to obtain (6E, 13E) -6, 13-bis ((4-bromophenyl) (4- (dodecyloxy) phenyl) methylene) -6, 13-pentacene quinone, namely a compound 7;
(6) Dissolving the compound 7 in an organic solvent J, carrying out illumination reaction under the action of iodine and propylene oxide under the protection of inert gas, removing the solvent and iodine simple substance after the reaction is finished, and purifying by column chromatography to obtain a compound 8, namely the target product dibromo-substituted hexabenzocoronene monomer;
the chemical structural formula of the compound 4 is as follows:
3. the method for preparing the dibromo-substituted hexabenzocoronene monomer according to claim 2, wherein in the step (1), the organic solvent A is acetonitrile or ethyl acetate, the base is potassium carbonate or sodium carbonate, the molar ratio of phenol, base and bromododecane is 1 (1.2-2): 1-1.1, the reaction temperature is 60-90 ℃ and the time is 12-24h; the anhydrous solvent B is dichloromethane, chlorobenzene, dichlorobenzene or trichlorobenzene, the molar ratio of anhydrous aluminum chloride to the compound 1 to 4-bromobenzoyl chloride is 1:1:1, the reaction temperature is 30-50 ℃, and the reaction time is 12-24 hours;
in the step (2), the organic solvent C is ethanol or n-amyl alcohol, the organic solvent D is tetrahydrofuran, dichloromethane or toluene, the reducing agent is hydrazine hydrate, the oxidizing agent is manganese dioxide, the molar ratio of the compound 2 to the reducing agent to the oxidizing agent is 1 (10-20) (8-15), the reaction temperature is 80-120 ℃, the reaction time is 12-24h, and the continuous reaction is carried out for 1-2h under the conditions of ice-water bath and light shielding;
in the step (3), the organic solvent E is toluene or chlorobenzene, the molar ratio of the compound 3 to the compound 4 to the triphenylphosphine is 1 (1.2-1.5), the continuous reaction temperature is 90-120 ℃, and the time is 12-48h;
in the step (4), the organic solvent F is formed by mixing acetone and methylene dichloride according to the volume ratio of 1-3:3, the organic solvent G is toluene or chlorobenzene, the oxidant is potassium permanganate, the molar ratio of the compound 5 to the oxidant to the Lawson reagent is 1 (2-4) (0.8-1.2), the reaction temperature is 85-100 ℃ under the protection of inert gas, and the reaction time is 1-3h;
in the step (5), the organic solvent H is tetrahydrofuran, methylene dichloride or toluene, the organic solvent I is toluene or chlorobenzene, the molar ratio of the compound 6 to the compound 3 to the triphenylphosphine is 1 (1.5-2) (1.2-1.5), the reaction temperature is 90-120 ℃ under the protection of inert gas, and the reaction time is 12-24 hours;
in the step (6), the organic solvent J is toluene, and the molar equivalent ratio of the iodine simple substance to the compound 7 is at least 10:1, the mol ratio of the epoxypropane to the compound 7 is (800-1100) 1, the light reaction is carried out under a high-pressure mercury lamp or an ultraviolet lamp, the reaction temperature is controlled to be not more than 40 ℃ in the light reaction process, and the time is 4-24 hours.
4. The hexabenzocoronene conjugated polymer prepared from the dibromo-substituted hexabenzocoronene monomer as claimed in claim 1, wherein the conjugated polymer has a chemical structural formula:
wherein R is C 1 –C 30 Alkyl or alkoxy of (a); x and y are integers between 0 and 100; n is an integer between 1 and 200; b is pi bridge unit; a is an electron acceptor unit.
5. The hexabenzocoronene conjugated polymer according to claim 4, wherein B is selected from any one of the following groups:
wherein X is O, S or Se; r is R 1 Is hydrogen、C 1 ～C 30 A linear or branched alkyl group of F, cl or CN.
6. The hexabenzocoronene conjugated polymer according to claim 4, wherein a is selected from any one of the following groups:
wherein R is 2 Is C 1 ～C 30 Straight or branched alkyl of (a); x is O, S or Se.
7. The method for preparing hexabenzocoronene conjugated polymer as defined in claim 4, wherein under the protection of inert gas, dibromo-substituted hexabenzocoronene monomer, dibromo-substituted A monomer and bis (trimethyltin) -substituted B monomer are dissolved in an organic solvent K, a catalyst is added for reaction, trimethyltin and bromobenzene are added for continuous reaction, after the reaction is finished, soxhlet extraction is carried out after methanol washing, and a ternary polymer is obtained after methanol recrystallization, thus obtaining the target product;
the chemical structural general formula of the dibromo-substituted A monomer is Br-A-Br, and the specific structural formula is as follows:
wherein R is 2 Is C 1 ～C 30 Straight or branched alkyl of (a); x is O, S or Se;
the chemical structural formula of the B monomer substituted by bis (trimethyltin) is (CH) 3 ) 3 Sn-B-Sn(CH 3 ) 3 The specific structural formula is as follows:
wherein X is O, S or Se; r is R 1 Is hydrogen, C 1 ～C 30 A linear or branched alkyl group of F, cl or CN.
8. The method for preparing hexabenzocoronene conjugated polymer according to claim 7, wherein the organic solvent K is chlorobenzene or toluene;
the catalyst is the combination of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphorus;
the extractant used in Soxhlet extraction is methanol, acetone, n-hexane and chloroform in this order.
9. The method for preparing the hexabenzocoronene conjugated polymer according to claim 7, wherein the molar ratio of the dibromo-substituted hexabenzocoronene monomer, the dibromo-substituted A monomer, the bis (trimethyltin) -substituted B monomer, the trimethyltin (phenyl) and the bromobenzene is x:y:1 (5-10): 5-10, wherein x+y=1;
the amounts of tris (dibenzylideneacetone) dipalladium and tris (o-methylphenyl) phosphorus were 0.02eq and 0.08eq, respectively.
10. The method for preparing hexabenzocoronene conjugated polymer according to claim 7, wherein the reaction temperature is 100-120 ℃ and the reaction time is 24-72h after adding the catalyst;
the temperature of the continuous reaction is 100-120 ℃ and the time is 24-48h.
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