CN116789942A - Conjugated polymer containing 9-phenoxy-10-phenylanthracene structural unit, and preparation method and application thereof - Google Patents
Conjugated polymer containing 9-phenoxy-10-phenylanthracene structural unit, and preparation method and application thereof Download PDFInfo
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- CN116789942A CN116789942A CN202310770784.5A CN202310770784A CN116789942A CN 116789942 A CN116789942 A CN 116789942A CN 202310770784 A CN202310770784 A CN 202310770784A CN 116789942 A CN116789942 A CN 116789942A
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- China
- Prior art keywords
- conjugated polymer
- anthracene
- phenoxy
- phenylanthracene
- polymer containing
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 52
- HQNNEBQFHVJLGJ-UHFFFAOYSA-N 9-phenoxy-10-phenylanthracene Chemical compound C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC=CC=C2C=1OC1=CC=CC=C1 HQNNEBQFHVJLGJ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- -1 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene Chemical compound 0.000 claims description 28
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 238000010523 cascade reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract description 7
- 125000000304 alkynyl group Chemical group 0.000 abstract description 6
- 125000005577 anthracene group Chemical group 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 49
- 239000000243 solution Substances 0.000 description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000012496 blank sample Substances 0.000 description 5
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 description 1
- OURODNXVJUWPMZ-UHFFFAOYSA-N 1,2-diphenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1C1=CC=CC=C1 OURODNXVJUWPMZ-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- BBSNJTOHVHUCRF-UHFFFAOYSA-N 1-bromo-4-[2-(4-bromophenyl)-1,2-diphenylethenyl]benzene Chemical group C1=CC(Br)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC(Br)=CC=1)C1=CC=CC=C1 BBSNJTOHVHUCRF-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- ONASMBRWDSADQY-UHFFFAOYSA-N 2-chloro-9,10-bis(4-methoxyphenyl)anthracene Chemical compound C1=CC(OC)=CC=C1C(C1=CC=C(Cl)C=C11)=C(C=CC=C2)C2=C1C1=CC=C(OC)C=C1 ONASMBRWDSADQY-UHFFFAOYSA-N 0.000 description 1
- PLMFIWDPKYXMGE-UHFFFAOYSA-N 2-chloro-9,10-diphenylanthracene Chemical group C=12C=CC=CC2=C(C=2C=CC=CC=2)C2=CC(Cl)=CC=C2C=1C1=CC=CC=C1 PLMFIWDPKYXMGE-UHFFFAOYSA-N 0.000 description 1
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical group C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
- 235000011447 Geum Nutrition 0.000 description 1
- 241000220313 Geum Species 0.000 description 1
- 241000083879 Polyommatus icarus Species 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XZDQYMBJMULIPV-UHFFFAOYSA-N [O-][N+](C(C=C1)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1OC(C=C1)=CC=C1[N+]([O-])=O)=O Chemical compound [O-][N+](C(C=C1)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1OC(C=C1)=CC=C1[N+]([O-])=O)=O XZDQYMBJMULIPV-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a conjugated polymer containing 9-phenoxy-10-phenyl anthracene structural unit, and a preparation method and application thereof. The conjugated polymer takes an asymmetrically modified large conjugated system anthracene unit as a main unit, and is connected with electron-rich donor units with good hole transmission and electron transmission performances such as phenyl, tetraphenyl ethylene, fluorene, carbazole and the like through alkynyl groups to jointly construct the D-pi-A conjugated polymer with good fluorescence performances, and the D-pi-A conjugated polymer has good solubility, chemical stability and good photoluminescence performances, and can be widely used as fluorescent materials or fluorescent probes.
Description
Technical Field
The invention relates to a conjugated polymer material, in particular to a conjugated polymer containing 9-phenoxy-10-phenyl anthracene structural unit with fluorescence performance, and a preparation method and application thereof, belonging to the technical field of functional polymer materials.
Background
Anthracene is a common blue fluorescent material and is formed by fusing three benzene rings, but because of a large aromatic ring conjugated system, molecules are easy to gather to form crystals, so that the application value of the anthracene in the field of luminescent materials is greatly reduced. Therefore, the prior researches mainly carry out structural modification on anthracene to reduce intermolecular aggregation and improve the thermal stability, crystallization performance and the like of the anthracene. Polyanthrylene is a polymer fluorescent material with good thermal stability, which is easy to process and form, and the luminous color can be adjusted, so that the polyanthrylene has been paid attention to by researchers.
Literature (Chen L, chen K Z, yao R J.from blue fluorescence to red fluorescence: solid-state oxidative coupling polymerization of fluorene and anthracene or naphthalene [ J)]Materials Chemistry and Physics,2022, 285:126083.) are disclosed as FeCl 3 A series of fluorene-anthracene copolymer (PFA) and fluorene-co-naphthalene copolymer (PFN) were synthesized as an oxidizing agent by solid phase oxidative coupling polymerization (see reaction formula 1). By FT-IR and 1 h NMR characterizes the structure of the copolymer, showing a random structure consisting of fluorene units and 9, 10-anthracene units or 1, 4-linked naphthalene units. All copolymers exhibit good thermal stability, and the optical properties can be adjusted by adjusting the ratio between fluorene and anthracene and naphthalene. Furthermore, the luminescence of polymers ranges from blue to red, which can be attributed to the variation in the effective conjugation length of the individual polymers and the formation of polymer aggregates. These unique properties make PFA potentially useful in the optoelectronic field.
Reaction formula 1:
literature (Kitagawa Y, naito A, fushimi K. Bright sky-blue fluorescence with high color purity: assembly of luminescent diphenyl-anthracene lutetium-based coordination polymer [ J ]. Rsc Advances,2021, 11:6604-6606.) discloses that polymers of lutetium coordinated dibenzoanthracene derivatives have blue fluorescence and high color purity by assembling diphenylanthracene and metal ion lutetium ion coordination polymers (see equation 2). It can be seen that its high color purity is based on a tightly packed crystal structure of coordination polymers with multiple CH-F interactions.
Reaction formula 2:
literature (Park H Y, geum N, ko J.chemiluminecent properties of polymeric blue fluorophores containing diphenylanthracene unit [ J ]. Dyes and Pigments,2002, 54:59-66.) discloses the synthesis of novel conjugated and non-conjugated alternating block copolymers 1 containing 9, 10-diphenyl-2-chloroanthracene groups in the backbone by the Williamson method (see equation 3). The luminescence properties including chemiluminescence were studied by uv-vis absorption spectroscopy and compared to the model fluorophore 9, 10-bis (4-methoxyphenyl) -2-chloroanthracene. The polymer shows blue photoluminescence of up to about 430nm in solution. The polymer shows good solubility in common organic solvents, is moderately stable under the peroxide oxidation condition, but has a slightly short fluorescence decay time, and can be seen by naked eyes to maintain chemiluminescence for more than l2 hours.
Reaction formula 3:
disclosure of Invention
In view of the drawbacks of the prior art, a first object of the present invention is to provide a conjugated polymer containing 9-phenoxy-10-phenylanthracene structural units, which has good solubility, chemical stability and good photoluminescence properties, and can be widely used as fluorescent materials or fluorescent probes.
The second object of the invention is to provide a preparation method of the conjugated polymer containing the 9-phenoxy-10-phenylanthracene structural unit, which is simple, mild in condition and low in cost, and is beneficial to mass production.
A third object of the present invention is to provide an application of a conjugated polymer containing 9-phenoxy-10-phenylanthracene structural units, which has an emission peak with a maximum intensity in the blue region of about 410 to 430nm, can be used as a photo-fluorescent material, and at the same time, can selectively recognize Fe in a solution system 3+ Has fluorescence quenching phenomenon, and can be used for detecting Fe 3+ Is used as the fluorescent probe.
In order to achieve the above technical object, the present invention provides a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit, which has the following repeating structural unit:
wherein,,
ar is selected from the following structural units:
the conjugated polymer containing 9-phenoxy-10-phenyl anthracene structural unit is a D-pi-A type polymer fluorescent material, which takes an asymmetrically modified anthracene unit as a main unit, and connects electron-rich donor units with good hole transmission and electron transmission performance such as phenyl, tetraphenyl ethylene, fluorene, carbazole and the like through alkynyl so as to jointly construct the D-pi-A type conjugated polymer with good fluorescent performance.
The conjugated polymer containing 9-phenoxy-10-phenyl anthracene structural unit has asymmetrically modified anthracene unit, and the asymmetrically modified large conjugated system greatly improves the intramolecular charge transfer, simultaneously, alkynyl is introduced into the large conjugated system, the alkynyl has certain electron accepting capability, and when the alkynyl is connected with the asymmetrically modified large conjugated system anthracene unit, the electron withdrawing capability of the whole anthracene unit is increased, and the intramolecular charge transfer is further improved, so that the fluorescent property of the conjugated polymer is facilitated to be realized. Meanwhile, alkynyl is used as pi bridge, and an asymmetrically modified anthracene main body unit and donor units with strong electron donating ability such as TPE and fluorene are connected, so that the thermal stability of the polymer and the high quantum yield of blue light emission can be further enhanced. In addition, the asymmetrically modified anthracene unit introduces an ether oxygen bond, has an asymmetric structure and a polar structure, and simultaneously introduces n-octyl into carbazole and fluorene units, thereby being beneficial to improving the solubility of the conjugated polymer and reducing the crystallization performance thereof and being beneficial to processing.
The invention also provides a preparation method of the conjugated polymer containing the 9-phenoxy-10-phenylanthracene structural unit, which comprises the following steps:
1) 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene with potassium iodide in NaNO 2 And diazotizing-iodized tandem reaction under the action of p-toluenesulfonic acid to obtain 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene;
2) 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene with trimethylsilylacetylene in PdCl 2 (PPh 3 ) 2 And under the catalysis of CuI, carrying out Sonogashira coupling reaction, and then carrying out K on the reaction product 2 CO 3 Carrying out trimethyl silicon-based removal reaction under the action of the catalyst to obtain 9- (4-ethynylphenoxy) -10- (4-ethynylphenyl) anthracene;
3) 9- (4-Acetylylphenoxy) -10- (4-Acetylylphenyl) anthracene with dihaloaryl monomer in PdCl 2 (PPh 3 ) 2 And performing Sonogashira coupling polymerization under the CuI catalysis effect to obtain the catalyst;
the dihaloaryl monomer is selected from:
x is bromine or iodine.
As a preferred embodiment, in step 1), 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is added to a solution in which toluene sulfonic acid is dissolved, cooled to a temperature below 0℃and NaNO is added 2 And KI, and reacting for 40-80 min at-5 ℃. Wherein, the solution dissolved with the toluene sulfonic acid is prepared by adding the toluene sulfonic acid into the mixed solution of acetonitrile and water, and mixing the mixture at 60 to 70 percentStirring at the temperature of between 0.4 and 0.6 hour.
As a preferred embodiment, the molar ratio of the methylbenzenesulfonic acid to the 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is (2.5 to 3.5): 1.
As a preferred embodiment, naNO 2 The molar ratio of the catalyst to 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is (2.0-2.5): 1.
As a preferred embodiment, the molar ratio of KI to 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is from (2.0 to 2.5): 1.
As a preferred embodiment, in the step 2), the molar ratio of 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene to trimethylsilylacethylene is 1 (2-3).
As a preferred embodiment, the Sonogashira coupling reaction conditions are: reacting for 8-12 h at 65-75 ℃.
As a preferable scheme, the conditions of the trimethyl silyl removal reaction are as follows: at room temperature, the reaction is carried out for 4 to 6 hours.
As a preferred embodiment, the Sonogashira coupling polymerization conditions are: reacting for 24-48 h at 75-85 ℃.
The invention also provides application of the conjugated polymer containing the 9-phenoxy-10-phenylanthracene structural unit, which is applied as a fluorescent material. The conjugated polymer has absorption peak in the ultraviolet light region of 302-372 nm and emission peak with maximum intensity in the blue light region of 410-430 nm in solution such as THF, which shows that the conjugated polymer has good photoinduced fluorescence performance and can be used as fluorescent material.
The invention also provides an application of the conjugated polymer containing the 9-phenoxy-10-phenylanthracene structural unit as Fe 3+ And (5) detecting fluorescent probe application. Conjugated polymer for Fe in complex metal ion solution system 3+ Has selective recognition (e.g. Cu) 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ 、Fe 3+ Etc.), and Fe 3+ Can quench the fluorescence of conjugated polymer in a solution system, thereby being used as Fe 3+ And (5) detecting fluorescent probe application.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The conjugated polymer of the invention shows good room temperature solubility in conventional organic solvents such as THF, DCM, DMF and the like, so that the conjugated polymer has good processing performance.
2) The fluorescent emission spectrum of the conjugated polymer in THF solution shows that an emission peak with maximum intensity appears in the range of about 410-430 nm, and the conjugated polymer can be used as fluorescent material.
3) The conjugated polymer has good chemical heat stability, and the 10% heat weight loss temperature is 350-492 ℃, so that the application requirements under different temperature environments can be met.
4) The energy gap values of the conjugated polymer are all about 3.0eV, and the conjugated polymer has good electrochemical performance.
5) The conjugated polymer of the invention can recognize Fe in THF solution 3+ Simultaneously, fluorescence quenching is accompanied, and the anti-interference performance is strong, cu 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ The plasma metal ion does not cause fluorescence quenching and can be used as Fe 3+ The fluorescent probe for detection is used.
6) The preparation method of the conjugated polymer is simple, mild in condition and low in cost, and is beneficial to expanding production.
Drawings
FIG. 1 is P8 1 H NMR spectrum.
FIG. 2 is P8 13 C NMR spectrum.
Fig. 3 is a FTIR spectrum of P8.
FIG. 4 is P9 1 H NMR spectrum.
Fig. 5 is a FTIR spectrum of P9.
FIG. 6 shows conjugated polymers P9 to P12 in THF solution (1X 10) –5 mol/L) fluorescence emission spectrum.
FIG. 7 shows conjugated polymers P9 to P12 in THF solution (1X 10) -5 mol/L) of PL spectra.
FIG. 8 shows the conjugated polymers P9 to P12 in solvents of different polarities (1X 10) –5 mol/L).
FIG. 9 is a CV curve of conjugated polymers P9-P12 in dry DCM.
FIG. 10 shows TGA curves of conjugated polymers P9 to P12 under nitrogen atmosphere.
FIG. 11 shows fluorescence spectra of conjugated polymers P9 to P12 in a metal ion tetrahydrofuran solution, 10. Mu.L of the conjugated polymers were prepared at a concentration of 1X 10 –2 mol/L metal hydrochloride MCl m (M＝Cu 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ 、Fe 3+ ) The fluorescence intensities thereof were respectively tested.
FIG. 12 shows a blank sample of conjugated polymer P9 without any metal ions added to tetrahydrofuran solution and a sample solution with different metal ions added thereto, respectively (blank sample, cu from left to right 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ 、Fe 3+ ) Photographs at 365nm uv light.
FIG. 13 shows the difference of Fe 3+ Fluorescence spectrum of P12 in tetrahydrofuran at concentration and its fluorescence emission coefficient change curve were measured in 1mL of THF solution (1X 10) –5 mol/L), 10. Mu.L (0.005-0.04). Times.10 are added respectively –2 Fe in the concentration range of mol/L 3+ A solution.
Detailed Description
The following specific examples are intended to illustrate the present invention in further detail, but are not intended to limit the scope of the claims.
The chemical starting materials referred to in the following examples are commercially available in the art unless specifically indicated.
The following examples are directed to conventional performance testing methods, and specific testing apparatus: nuclear magnetic resonance spectrometer, bruker Vance, switzerland; fourier infrared spectrometer, U.S. Perkin-Elmer Spectrum One FTIR spectrometer; steady state transient fluorescence spectrometer, edinburgh, inc. in UK; thermogravimetric analysis, shimadzu DT-40 thermal analyzer; electrochemical workstation, shanghai Chenhua instruments Co., ltd; ultraviolet visible absorption spectrometer, hitachi.
The specific equations referred to in the following specific examples are as follows:
m1 and M2 are synthesized with reference to the prior art literature:
preparation of 9- (4-nitrophenoxy) -10- (4-nitrophenyl) anthracene M1:
to a 100mL three-necked flask were added anthrone (5.82 g,30 mmol), p-fluoronitrobenzene (9.31 g,66 mmol), potassium tert-butoxide (6.72 g,60 mmol), and 60mL DMF. At N 2 Under the atmosphere, the reaction is carried out for 36 hours at 120 ℃, after the reaction is stopped, the reaction solution is cooled to room temperature, slowly poured into 200mL of ice water, brown yellow solid is separated out, the crude product is obtained by filtration, and 7.13g of yellow solid is obtained by drying and column chromatography separation in sequence, and the yield is 80%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝8.50(d,J＝8.4Hz,2H),8.20(d,J＝9.2Hz,2H),8.07(d,J＝8.4Hz,2H),7.69(d,J＝8.4Hz,2H),7.61(d,J＝8.8Hz,2H),7.49(t,J＝7.0Hz,2H),7.44(t,J＝7.6Hz,2H),6.99(d,J＝9.2Hz,2H). 13 CNMR(100MHz,CDCl 3 ):δ(ppm)＝164.2,147.6,145.3,144.8,142.7,130.2,126.9,126.7,126.3,126.1,123.9,121.8,115.6.
Preparation of 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene M2:
at N 2 M1 (3.76 g,8.6 mmol), pd/C (0.31 g), hydrazine hydrate (6.5 mL) and ethanol (80 mL) were charged to a 250mL three-necked flask under an atmosphere and reacted at 70℃for 24 hours. After the reaction was completed, the filter cake was dissolved in DCM, concentrated and the residue was separated by column chromatography (PE/EA as eluent, V/v=25:1) to give 3.31 as a yellow solid g in 80% yield. 1 H NMR (400 MHz, DMSO): δ (ppm)＝8.08(d,J＝8.4Hz,2H),7.77(d,J＝8.7Hz,2H),7.44(dt,J＝14.0,6.6Hz,4H),7.09(d,J＝8.2Hz,2H),6.83(d,J＝8.3Hz,2H),6.55(s,2H),6.49(d,J＝8.9Hz,2H),5.31(s,2H),4.71(s,2H). 13 C NMR(100MHz,DMSO):δ(ppm)＝151.97,148.69,145.50,145.38,143.92,135.42,132.15,131.24,127.56,126.05,125.94,124.77,122.60,115.90,115.49,114.39.
Example 1
Preparation of 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene M3:
into a 100mL three-necked flask, p-toluenesulfonic acid (1.55 g,9 mmol) and a mixed solution of acetonitrile and water were added, respectively, and reacted at 60℃for 0.5h, followed by addition of M2 (1.13 g,3 mmol), followed by cooling to 0℃and addition of NaNO 2 (0.97 g,6 mmol), KI (0.41 g,6 mmol) and H 2 O is prepared into a solution, the reactant is reacted for 1h at the temperature of 0 ℃, then the temperature is raised to the room temperature, and the reaction is continued for 2h. After the reaction, the reaction mixture was poured into 150mL of water, naHCO was added 3 Adjusting pH of the mixture to alkalescence, and adding appropriate amount of Na 2 S 2 O 3 Stirring for 10min, extraction with DCM, combining the organic phases, drying over anhydrous magnesium sulfate and removing the solvent. The mixture was purified by column chromatography using n-hexane/DCM as eluent (V/v=100/1) to give 0.72g as a white powder with a yield of 60%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝8.08(d,J＝8.5Hz,2H),7.93(d,J＝8.1Hz,2H),7.67(d J＝8.6Hz,2H),7.52(d,J＝8.7Hz,2H),7.39(dt,J＝15.0,6.7Hz,4H),7.21(d J＝8.1Hz,2H),6.65(d,J＝8.7Hz,2H),5.31(s,2H),4.71(s,2H). 13 C NMR(100MHz,CDCl 3 ):δ(ppm)＝160.03,145.11,138.66,137.98,137.71,133.59,133.37,130.74,126.84,125.98,125.92,124.23,122.25,117.75,93.56,84.24.
Example 2
Preparation of 9- (4-ethynylphenoxy) -10- (4-ethynylphenyl) anthracp 8:
at N 2 In the environment, M3 (1.2 g,2 mmol) and PdCl were added to a 100mL three-necked flask 2 (PPh 3 ) 2 (36.1 mg,0.05 mmol) and CuI (38.09 mg,0.2 mmol), and then 20mL of a mixed solution of triethylamine and tetrahydrofuran (V/V=30/11) were added, and the reaction was continued at 70℃for 1 hour, and then trimethylsilylacetylene (0.39 g,4 mmol) was addedThe reaction was carried out for 10 hours. Stopping the reaction, cooling the reaction solution to room temperature, removing the solvent, and adding K 2 CO 3 And THF (15 mL) at room temperature for 5h. After stopping the reaction, the reaction solution was poured into 150mL of water, extracted with DCM, the organic phases were combined, dried over anhydrous magnesium sulfate and the solvent was removed. The mixture was purified by column chromatography using n-hexane/DCM (V/v=20/1) as eluent to give 0.41g of pale yellow powder in 41% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝8.00(d,J＝8.2Hz,2H),7.64(d,J＝7.8Hz,2H),7.58(d,J＝8.6Hz,2H),7.34(d,J＝7.7Hz,2H),7.30(dd,J＝8.0,4.5Hz,4H),7.26(d,J＝7.0Hz,2H),6.74(d,J＝8.6Hz,2H),3.10(s,1H),2.89(s,1H). 13 C NMR(100MHz,CDCl 3 ):δ(ppm)＝160.44,145.08,139.19,134.05,133.95,132.27,131.51,130.73,126.87,125.94,125.89,124.27,122.26,121.63,115.64,115.47,83.53,83.35.
Fig. 1 to 3 are a hydrogen spectrum, a carbon spectrum, and an FTIR spectrum of the small molecule P8, respectively. In the hydrogen spectrum of FIG. 1, it can be seen that single peaks appear at 3.100ppm and 2.893ppm, which are characteristic peaks of ≡C-H, with shifts in alkyne hydrogen at higher fields than alkene hydrogen. The proton displacement of the aromatic ring is in the range of 6-9 ppm, and the number and displacement of the hydrogen atoms in the spectrogram are consistent with the expected hydrogen atoms.
In the carbon spectrum of FIG. 2, it can be seen that characteristic peaks of C.ident.C appear at chemical shifts of 83.55ppm and 83.35ppm, and other peaks at chemical shifts of 110ppm to 165ppm are ascribed to carbons on the aromatic ring.
In the FTIR spectrum of FIG. 3, at 2108cm –1 The expansion vibration absorption peak of C.ident.C appears at 3292cm –1 What appears is the stretching vibration absorption peak of the ≡c-H bond. At 1592cm –1 、1500cm –1 、1437cm –1 The absorption peak is the stretching vibration peak of carbon-carbon double bond on the aromatic ring skeleton, 833cm –1 、773cm –1 、718cm –1 And 707cm –1 And the telescopic vibration absorption peak of=c-H on the aromatic ring.
According to the analysis, the structures shown by the three spectrograms are consistent with the structural characteristics of the compound P8.
Example 3
Synthesis of dihaloaryl monomers reference is made to the prior art literature:
preparation of 1, 2-bis (4-bromophenyl) -1, 2-diphenylethylene 1 b:
the preparation method comprises the following steps: a250 mL three-necked flask was charged with 4-bromobenzophenone (6.53 g,25 mmol) and zinc powder (3.25 g,50 mmol) in THF (100 mL) under nitrogen. The reaction solution was cooled to 0℃in an ice bath, and 2.8mL of TiCl was slowly added dropwise thereto 4 (4.74 g,25 mmol) and after the completion of the dropwise addition, the reaction mixture was heated to 25℃and reacted for 1 hour, and then heated to 70℃and reacted for 12 hours. After the reaction, the reaction mixture was slowly poured into 10% K 2 CO 3 In aqueous solution, suction filtration, extraction of the filtrate with DCM, combining the organic phases and washing 3 times with saturated solution of sodium chloride, drying over anhydrous magnesium sulfate and removal of the solvent. N-hexane is used as an eluent, and the white solid 1b is obtained through column chromatography separation and purification, and the yield is 65%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝7.29–7.20(m,4H),7.17–7.09(m,6H),7.03–6.96(m,4H),6.91–6.85(m,4H).
Preparation of 3, 6-dibromo-N-N-octylcarbazole 1 c:
the preparation method comprises the following steps: to a 250mL three-necked flask, 3, 6-dibromocarbazole (8.13 g,25 mmol), a 50% potassium hydroxide solution (12 mL), tetrabutylammonium bromide (2.27 g,7 mmol) and toluene (120 mL) were successively added, and the mixture was reacted at 110℃for 2 hours, followed by dropwise addition of 1-bromooctane (2.28 mL,30 mmol) and the reaction was continued for 30 hours. After stopping the reaction, the reaction solution was cooled to room temperature, poured into 200mL of water, extracted with DCM, the organic phases were combined, dried over anhydrous magnesium sulfate and the solvent was removed. N-hexane is used as an eluent, and the white solid 1c is obtained through column chromatography separation and purification, and the yield is 63%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝8.13(d,J＝1.7Hz,2H),7.55(dd,J＝8.7,1.8Hz,2H),7.25(s,2H),4.23(t,J＝7.2Hz,2H),1.86–1.79(m,2H),1.26(dd,J＝19.1,13.8Hz,10H),0.86(t,J＝6.8Hz,3H).
Preparation of 2, 7-dibromo-9-dioctylfluorene 1 d:
the preparation method comprises the following steps: to a 250mL three-necked flask, 2, 7-dibromofluorene (9.23 g,28 mmol), KOH (9.56 g,168 mmol), KI (0.470 g,2.85 mmol) and DMSO (70 mL) were added, and the mixture was reacted at 0℃for 30 minutes, followed by 1-bromooctane (13.77 g,57 mmol) and then slowly warmed to 25℃to react for 36 hours after the completion of the addition. After the reaction was stopped, the reaction mixture was poured into 300mL of water, extracted with ethyl acetate, and the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed. N-hexane is used as an eluent, and the white solid 1d is obtained through column chromatography separation and purification, and the yield is 65%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝7.51(d,J＝8.5Hz,2H),7.44(d,J＝7.5Hz,4H),1.94–1.87(m,4H),1.23–1.03(m,20H),0.83(t,J＝7.1Hz,6H),0.59(s,4H).
Example 4
The preparation method of the polymer comprises the following steps: taking P9 as an example, in N 2 In a 25mL three-necked flask, a terminal alkyne monomer P8 (1.2 g,3 mmol), P-dibromobenzene (0.72 g,3 mmol), cuI (57.14 mg,0.3 mmol) and PdCl were sequentially introduced under the circumstance 2 (PPh 3 ) 2 (35.1 mg,0.05 mmol) and DMF (5 mL) were reacted at 80℃for 36h. After the reaction was completed, the reaction solution was slowly poured into a methanol solution to precipitate a brown solid, which was suction-filtered and dried, and the obtained solid was sequentially extracted with methanol and acetone in each of the soxhlet extractors for 12 hours, and vacuum-dried to obtain 0.46g of brown solid. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)＝8.11(s,2H),7.85–7.61(m,5H),7.44(s,10H),6.88(s,3H).
The synthesis method of P10 to P12 refers to the synthesis method of P9.
As shown in FIG. 4, which shows the hydrogen spectrum of polymer P9, it can be seen that the proton shifts on the aromatic rings are all between 6 and 9ppm, and the number of hydrogen is consistent with the expected number of polymer hydrogens. FIG. 5 is a Fourier infrared spectrum of Polymer P9 at 2350cm –1 The small peak is a telescopic vibration absorption peak of a carbon-carbon triple bond, 3292cm –1 The stretching vibration absorption peak of the ≡c-H bond appearing at the site also disappeared, proving that no cleavage of the carbon-carbon triple bond occurred during the polymerization, and the polymerization was successful.
Example 5
Characterization of the properties of the conjugated polymers P9 to P12 prepared in example 4:
ultraviolet absorption spectrum:
FIG. 6 shows the polymers P9 to P12 in THF solution (1X 10) –5 mol L -1 ) Is a uv-vis absorption spectrum of (a). As shown in FIG. 6, the UV-visible absorption spectra of P9 and P11 exhibited two main absorption peaks at 298nm and 372nm, respectively. The three main absorption peaks are shown by P10 and P12, and are respectively about 302nm and 334nm and 372nm. The absorption bands of the polymers P9 to P12 at 372nm may be pi-pi of anthracene * And (5) transition. The uv maximum absorption peaks of P12 and P10 are red shifted by about 35nm compared to P9 and P11, probably due to the introduction of tetraphenylvinyl, 9-dioctylfluorene, which increases the conjugation degree of the whole polymer, resulting in a red shift of the uv absorption peaks of polymers P12 and P10.
Fluorescence emission spectrum:
FIG. 7 is a graph of fluorescence emission spectra of polymers P9 to P12 in THF solution, with an emission peak of maximum intensity in the range of 415 to 425nm, and the solution emitting blue fluorescence. The fluorescence emission wavelength of the polymer introduced with structural units such as benzene ring, tetraphenyl ethylene, fluorene, carbazole and the like has little change. The series of polymers fluoresce to varying degrees in most solvents, but emit little light in the solid state, showing a pronounced ACQ phenomenon, which may be caused by the formation of intermolecular aggregation states.
The polymers P9 to P12 are fluorescent in most organic solvents, but the solvation effect has different effects on the luminescence performance due to the different structures of the polymers P9 to P12. FIG. 8 is a fluorescence emission spectrum of polymers P9 to P12 in solvents of different polarities. The fluorescence emission wavelength of P9 and P12 does not change significantly along with the increase of the polarity of the solution, the effect of the polarity of the solution is less, the fluorescence emission wavelength of P9 is in the range of 429-440 nm, the fluorescence emission wavelength of P12 is in the range of 414-426 nm, the fluorescence emission wavelengths of the polymers P9-P12 in the five solutions with different polarities do not show obvious rules, and the effect of solvation is not affected.
It can be seen that the polymers P10 and P11 have a significant blue shift in DMSO solution, with maximum fluorescence emission wavelengths of 427nm and 415nm, respectively, which may be due to the fact that the energy difference between the ground state and the excited state is increased by the polar aprotic solvent, resulting in a shift of the fluorescence maximum emission wavelength in the short-wave direction, and thus a blue shift. The maximum fluorescence emission wavelength of the series of polymers is less affected by the polarity of the solution.
Polymer electrochemical properties:
electrochemical properties of tables 1P9 to P12
a The onset of oxidation potentials relative to Fc/Fc + couple.
b Determined from E onset ox.
c Estimated from E onset ox and E g .
e E g e ＝E LUMO –E HOMO
Electrochemical properties of polymers P9-P12 in dry DCM were studied using Cyclic Voltammetry (CV), whose CV curves are shown in fig. 9, and corresponding electrochemical data are listed in table 1. As can be seen from Table 1, the first oxidation potential (E onset ) 1.92eV, 1.52eV, 1.71eV, 1.04eV, respectively. According to [ E ] HOMO ＝-(4.8+E onset –E Fc/Fc+ )eV](E Fc/Fc+ ＝0.4eV，F c Representing ferrocene) and [ E ] LUMO ＝(E HOMO +Eg)eV(E g 1240/λ, λ is the initial wavelength of the uv-vis absorption spectrum]Two ofEquation, its molecular orbital level (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are calculated. The highest occupied molecular orbital energy levels of the polymers P9-P12 are respectively-6.32 eV, -5.92eV, -6.11eV and-5.44 eV. The energy levels of the lowest unoccupied molecular orbitals are-3.31 eV, -2.90eV, -3.10eV and-2.45 eV respectively.
Polymer thermodynamic properties:
the series of polymers P9 to P12 were tested for their thermal stability by thermogravimetric analysis (TGA). FIG. 10 shows that polymers P9 to P12 are in N 2 A thermal degradation process from 20 ℃ to 800 ℃ in the environment. As can be seen in fig. 10, the series of polymers has excellent thermal stability. Polymers P9 and P12 have a 5% weight loss temperature above 200deg.C, and polymers P10 and P11 have a 5% weight loss temperature around 400deg.C; the thermal weight loss temperature of the four polymers P9-P12 is above 350 ℃ at 10%, and the polymer P10 reaches 492 ℃. In addition to the polymer P12, other polymers can retain more than 72% of their weight when heated to 800 ℃. The fluorescent polymers of the series have excellent thermal stability, and have great application value in the aspect of photoelectric devices.
Fluorescence properties of polymers P9 to P12 for metal ions:
under the room temperature condition, the selectivity of the polymers P9 to P12 to different metal ions is studied by using a fluorescence spectrometer. As can be seen from FIG. 11, in 1mL of tetrahydrofuran solution of polymers P9 to P12 (1X 10 –5 mol/L), 10. Mu.L of the prepared concentration of 1X 10 was added to each of the above –2 mol/L metal hydrochloride MCl m (M＝Cu 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ 、Fe 3+ ) The fluorescence intensities thereof were respectively tested. As can be seen from the fluorescence emission spectra of polymers P9-P12, zn was added 2+ 、Na + 、Ba 2+ 、K + And Ca 2+ The fluorescence intensity of the solution of the samples of the five ions is weakened to different degrees. But with Fe 3+ And Cu 2+ The addition of two metal ions leads to a significant change in fluorescence emission spectrum and contains Fe 3+ And Cu 2+ Two metal ions are dissolvedThe maximum fluorescence intensity of the liquid almost disappeared. FIG. 12 is a blank sample of polymer P9 without any metal ions added to the tetrahydrofuran solution and a sample solution with different metal ions added separately (blank sample, cu from left to right 2+ 、Zn 2+ 、Na + 、Ba 2+ 、K + 、Ca 2+ 、Fe 3+ ). Photograph under 365nm ultraviolet light, clearly seen, with Cu 2+ And Fe (Fe) 3+ The fluorescence of the added solution changes, and the added solution contains Fe 3+ Quenching the fluorescence of the sample solution containing Fe 3+ Contains Cu as compared with the solution of 2+ Still weak blue fluorescence.
Metal ion sensitivity:
overall, the series of polymers is specific to Fe 3+ The response is more acute, so taking the polymer P12 as an example, the polymer P12 is used for researching Fe by a fluorescence titration experiment 3+ Is a detection sensitivity of (a). After 1mL of polymer P12 in THF (1X 10 –5 mol/L), 10. Mu.L of 0.005-0.04X10 are added respectively –2 Fe in the concentration range of mol/L 3+ A solution. As shown in fig. 13, with Fe 3+ The concentration of (2) gradually increases and the fluorescence intensity of the sample solution gradually decreases.
At low concentrations of analyte, its fluorescence response capability can be analyzed by the Stern-Volmer equation. The Stern-Volmer equation is as follows: i 0 /I＝1+K[Q]，I 0 The fluorescence intensity without adding iron ions, I is the fluorescence intensity with adding iron ions, K is the Stern-Volmer quenching constant, [ Q ]]Is the concentration of iron ions.
The detection limit formula is as follows: lod=3σ/K, where LOD is the limit of detection, σ is the standard deviation of the blank probe sample measurement, and K is the slope of the fitted curve. The limit of detection was calculated by fluorescence titration and the solution of P12 in tetrahydrofuran (1X 10) was measured by fluorescence emission spectrometer –5 mol/L) was measured 10 times, and the standard deviation sigma of the blank sample measurement was obtained.
Fitting linear equation for P12 obtained by the Stern-Volmer equation: i 0 /I＝1.3092+29.067[Fe 3+ ](R 2 = 0.9875), and calculates the LOD thereof to be 1.03×10 –5 mol/L, indicating that polymer P12 is relative to Fe 3+ Has good detection sensitivity.
Claims (10)
1. A conjugated polymer comprising 9-phenoxy-10-phenylanthracene structural units, characterized in that: has the following repeating structural units:
wherein,,
ar is selected from the following structural units:
2. a process for the preparation of a conjugated polymer containing 9-phenoxy-10-phenylanthracene structural units according to claim 1, characterized in that: the method comprises the following steps:
1) 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene with potassium iodide in NaNO 2 And diazotizing-iodized tandem reaction under the action of p-toluenesulfonic acid to obtain 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene;
2) 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene with trimethylsilylacetylene in PdCl 2 (PPh 3 ) 2 And under the catalysis of CuI, carrying out Sonogashira coupling reaction, and then carrying out K on the reaction product 2 CO 3 Carrying out trimethyl silicon-based removal reaction under the action of the catalyst to obtain 9- (4-ethynylphenoxy) -10- (4-ethynylphenyl) anthracene;
3) 9- (4-Acetylylphenoxy) -10- (4-Acetylylphenyl) anthracene with dihaloaryl monomer in PdCl 2 (PPh 3 ) 2 And performing Sonogashira coupling polymerization under the CuI catalysis effect to obtain the catalyst;
the dihaloaryl monomer is selected from:
x is bromine or iodine.
3. The method for producing a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit according to claim 2, wherein: in step 1), 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is added into a solution in which toluene sulfonic acid is dissolved, cooled to a temperature below 0 ℃, and then NaNO is added 2 And KI, and reacting for 40-80 min at-5 ℃.
4. A process for the preparation of a conjugated polymer containing 9-phenoxy-10-phenylanthracene structural units according to claim 3, characterized in that:
the molar ratio of the methylbenzenesulfonic acid to the 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is (2.5-3.5): 1;
NaNO 2 the molar ratio of the N-amino-benzene to the 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is (2.0-2.5): 1;
the molar ratio of KI to 9- (4-aminophenoxy) -10- (4-aminophenyl) anthracene is (2.0-2.5): 1.
5. The method for producing a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit according to claim 2, wherein: in the step 2), the molar ratio of 9- (4-iodophenoxy) -10- (4-iodophenyl) anthracene to trimethylsilylacethylene is 1 (2-3).
6. The method for producing a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit according to claim 2 or 5, wherein: the conditions of the Sonogashira coupling reaction are as follows: reacting for 8-12 h at 65-75 ℃.
7. The method for producing a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit according to claim 2, wherein: the conditions of the trimethyl silicon-based removal reaction are as follows: at room temperature, the reaction is carried out for 4 to 6 hours.
8. The method for producing a conjugated polymer containing a 9-phenoxy-10-phenylanthracene structural unit according to claim 2, wherein: the conditions of the Sonogashira coupling polymerization are as follows: reacting for 24-48 h at 75-85 ℃.
9. Use of a conjugated polymer comprising 9-phenoxy-10-phenylanthracene structural units according to claim 1, characterized in that: as fluorescent materials.
10. Use of a conjugated polymer comprising 9-phenoxy-10-phenylanthracene structural units according to claim 1, characterized in that: as Fe 3+ And (5) detecting fluorescent probe application.
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