CN112592709B - 一种基于硼簇阴离子光致变色材料的制备方法 - Google Patents
一种基于硼簇阴离子光致变色材料的制备方法 Download PDFInfo
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- CN112592709B CN112592709B CN202011478159.6A CN202011478159A CN112592709B CN 112592709 B CN112592709 B CN 112592709B CN 202011478159 A CN202011478159 A CN 202011478159A CN 112592709 B CN112592709 B CN 112592709B
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001450 anions Chemical class 0.000 title claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 13
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 7
- MGFJDEHFNMWYBD-UHFFFAOYSA-N 4-(2-pyridin-4-ylethenyl)pyridine Chemical group C=1C=NC=CC=1C=CC1=CC=NC=C1 MGFJDEHFNMWYBD-UHFFFAOYSA-N 0.000 claims description 5
- CBMYFVSIIYILRH-UHFFFAOYSA-N 2,4,6-tri-4-pyridyl-1,3,5-triazine Chemical compound C1=NC=CC(C=2N=C(N=C(N=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 CBMYFVSIIYILRH-UHFFFAOYSA-N 0.000 claims description 4
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 claims description 4
- UOSYDSDIRAXTTF-UHFFFAOYSA-N 2,4,6-tripyridin-3-yl-1,3,5-triazine Chemical compound C1=CN=CC(C=2N=C(N=C(N=2)C=2C=NC=CC=2)C=2C=NC=CC=2)=C1 UOSYDSDIRAXTTF-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 50
- 230000008859 change Effects 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000000862 absorption spectrum Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 2
- 230000036211 photosensitivity Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 230000005284 excitation Effects 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 150000001638 boron Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 239000000370 acceptor Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VVULXZDDIRIASU-UHFFFAOYSA-N N1=NN=CC=C1.CC=1NC=CN1.CC=1NC=CN1.CC=1NC=CN1 Chemical compound N1=NN=CC=C1.CC=1NC=CN1.CC=1NC=CN1.CC=1NC=CN1 VVULXZDDIRIASU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000001988 diarylethenes Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- -1 spirooxazine Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
本发明公开了一种基于硼簇阴离子光致变色材料的制备方法,将共轭性多吡啶分子加入超纯水中,然后用无机酸将pH调节至‑1~7,并在室温下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有硼簇化合物的水溶液加入溶液A中,生成沉淀后继续搅拌0.5~24h,过滤获得沉淀物,洗涤、真空干燥得到基于硼簇阴离子的光致变色材料。本发明反应条件温和,工艺简便易操作。材料变色前后吸收光谱区别大、制备成本低。合成的材料具有更高的光敏感性,变色更快,自由基寿命更长。为后续利用此类光致变色材料于生物治疗、光电转化等应用领域提供了借鉴思路,在光电催化方面具有很大的应用前景。
Description
技术领域
本发明属于材料技术领域,具体涉及一种基于硼簇阴离子光致变色材料的制备方法。
背景技术
有机光致变色是指两个异构体分子之间可逆的光诱导转化,光照前后两种异构体的吸收光谱有明显区别。在光异构化这个可逆的过程中,光致变色化合物的某些物理性质,例如紫外吸收光谱、分子共轭程度、荧光发射光谱、电导率、磁性、配位性、偶极相互作用、电化学性质、折射率等等可能会发生改变。这就启发人们把这类化合物应用在各个领域,例如分子开关、数据记录与存储、多光子器件、纳米粒子器件、光电等领域。
有机光致变色原理一般有价键异构、键的断裂、氧化还原以及二聚体的形成等;在过去的研究中也主要围绕着螺噁嗪类、二芳基乙烯类以及偶氮苯类等传统有机光致变色化合物展开,采用的方法一般有衍生功能化、聚合物接枝、掺杂无机金属等。这些改性的材料所带来的性质的改变仍然有限,仍很难达到实际应用的要求。例如材料合成繁琐、价格昂贵、激发波长短等等。所以发展更多类型的光致变色材料已经引起了众多科学家们的注意。
光诱导电子迁移(PhotoinducedElectronTransfer,PET)是指在光激发下,电子从电子给体迁移到电子受体,并生成电子给体自由基和电子受体自由基的过程。具有光诱导电子迁移性能的材料在化学科学与材料技术的许多分支领域,例如光电转换、人工光合成、光催化中都有着十分广泛的应用。
电子迁移型光致变色材料与二芳基乙烯、螺吡喃等传统的变色材料相比具有以下优点:1.电子给体和电子受体可以通过氢键、分子间作用力、配位键进行组装,避免了繁琐的有机合成;2.通过修饰电子给受体及它们的组装方式可以得到性能可控的变色材料;3.可形成聚合物材料,与传统光色单分子相比具有更高的热稳定性、更长的变色时间。报道的有机光致变色材料存在多种多样的问题,例如合成繁琐、成本高、激发波长小、量子产率低等缺点。
发明内容
本发明目的在于提供一种新型D-A(Donor-Acceptor)结构具有光电性质材料的制备方法,所得材料具有变色前后吸收光谱区别大、合成及其简便、成本低、自由基寿命长等优点。
为达到上述目的,采用技术方案如下:
一种基于硼簇阴离子光致变色材料的制备方法,包括以下步骤:
将共轭性多吡啶分子加入超纯水中,然后用无机酸将pH调节至-1~7,并在室温下超声搅拌直至溶液完全澄清透明,得到溶液A;
将含有硼簇化合物的水溶液加入溶液A中,生成沉淀后继续搅拌0.5~24h,过滤获得沉淀物,洗涤、真空干燥得到基于硼簇阴离子的光致变色材料。
按上述方案,所得溶液A的浓度为0.01~150mmol/L。
按上述方案,硼簇化合物与共轭性多吡啶分子的摩尔比为1:(0.01~100)。
按上述方案,所述硼簇化合物的阳离子为钠、钾、铯中的一种;阴离子为1-氟十一氢十二硼烷([B12H11F]2-)、1-氯十一氢十二硼烷([B12H11Cl]2-)、1-溴十一氢十二硼烷([B12H11Br]2-)、1-碘十一氢十二硼烷([B12H11I]2-)、1-氨基十一氢十二硼烷([B12H11NH3]-)、1-羟基十一氢十二硼烷([B12H11OH]2-)、十二氟十二硼烷([B12F12]2-)、十二氯十二硼烷([B12Cl12]2-)、十二溴十二硼烷([B12Br12]2-)、十二碘十二硼烷([B12I12]2-)、十二羟基十二硼烷([B12(OH)12]2-)、十二氢十二硼烷([B12H12]2-)、十氢十硼烷([B10H10]2-)中的一种。
按上述方案,所述共轭性多吡啶分子为2,4,6-三(吡啶-4-基)-1,3,5-三嗪(TPT)、2,4,6-三(吡啶-3-基)-1,3,5-三嗪、2,4,6-三(吡啶-2-基)-1,3,5-三嗪、甲基紫精、1,2-二(吡啶-4-基)乙烯、2,2-联吡啶、4,4-联吡啶、邻菲罗啉、三嗪三咪唑、三-(甲基咪唑)-三嗪中的一种。
按上述方案,所述无机酸为盐酸、硫酸、磷酸中的一种。
在众多的硼簇化合物中,十二氢十二硼烷阴离子是理论上最稳定的一类硼簇。closo-[B12H12]2-是一种正二十面体闭式笼状结构,具有高度对称的特性,十二个硼原子等同,氢原子比较容易被其他官能团取代,例如氟、氯、溴、碘、羟基、氨基等,从而获得具有各种特性的硼簇衍生物,如:1-氟十一氢十二硼烷([B12H11F]2-)、1-氯十一氢十二硼烷([B12H11Cl]2-)、1-溴十一氢十二硼烷([B12H11Br]2-)、1-碘十一氢十二硼烷([B12H11I]2-)、1-氨基十一氢十二硼烷([B12H11NH3]-)、1-羟基十一氢十二硼烷([B12H11OH]2-)、十二氟十二硼烷([B12F12]2-)、十二氯十二硼烷([B12Cl12]2-)、十二溴十二硼烷([B12Br12]2-)、十二碘十二硼烷([B12I12]2-)、十二羟基十二硼烷([B12(OH)12]2-)等。
以下为closo-[B12H12]2-衍生出的各种衍生物,其中,a:B-X键;b:B-S键;c:B-O键;d:B-N键;e:B-C键;f:B-P键和B-As键;g:B-S键;h:B-金属衍生物。所有衍生物只列出单取代情况。
本发明充分利用了硼簇的“3D芳香性”与多吡啶分子大的共轭结构,构建了一类新型D-A结构的具有光电性质的材料,在该材料中,硼簇表现出三维电子离域结构,并具有一定的给电子特性,成为新一类电子供体(Donor),这是硼簇在光电材料领域所走出的重要一步。该材料具有变色前后吸收光谱区别大、合成及其简便、成本低、自由基寿命长等优点。
相对于现有技术,本发明的有益效果在于:
反应条件温和,工艺简便易操作。
材料变色前后吸收光谱区别大、制备成本低。
合成的材料具有更高的光敏感性,变色更快,自由基寿命更长。
为后续利用此类光致变色材料于生物治疗、光电转化等应用领域提供了借鉴思路,在光电催化方面具有很大的应用前景。
具体实施方式
以下实施例进一步阐释本发明的技术方案,但不作为对本发明保护范围的限制。
实施例1
本发明所用的几种共轭性多吡啶分子的制备:
(1)2,4,6-三(吡啶-4-基)-1,3,5-三嗪(TPT)的制备
将4-氰基吡啶(6.0g,56mmol)加入100mL三颈烧瓶中并在油浴中加热到150℃。向所得的液体中添加粉末状的NaOH(230mg,5.6mmol),并将混合物在150℃下继续保持24h,反应结束后冷却到室温,固体用大量的丙酮洗涤并溶解在50mL 4M的盐酸中,然后加入活性炭超声处理30分钟。将悬浮液用硅藻土过滤,滤下用2mol/LNaOH溶液中和,此时会产生大量的白色沉淀,过滤后用大量水和丙酮交替各洗涤三次,60℃烘箱干燥。得到产品,为白色固体(3.1g,产率52%)。
(2)2,4,6-三(吡啶-3-基)-1,3,5-三嗪的制备
将4-氰基吡啶(10.0g,96mmol),18-crown-6(1.00g,3.8mmol),氢氧化钾(225mg,4.0mmol)和十氢化萘10mL混合物于200℃在氩气下搅拌5小时。反应冷却至室温后,将混合物过滤,然后用热吡啶洗涤几次(5×50mL),得到浅黄色至白色粉末。将固体溶解在的1M盐酸中,并用氨水再沉淀。过滤沉淀物,并用去离子水洗涤至中性。烘干得到产物5.4g(产率约54%)。
(3)2,4,6-三(吡啶-2-基)-1,3,5-三嗪的制备
将6g 2-氰基吡啶加入50mL三口烧瓶中,通氮气10min钟后,向其中小心地加入氢化钠。氮气氛围下165℃加热反应5小时。反应结束后,冷却到室温,用热的苯萃取反应混合物,并从乙醇-水中重结晶,烘干后得到产物3g(产率45%)。
(4)甲基紫精的制备
称取20mmol 4,4-联吡啶加入到装有60mL乙腈的单口烧瓶中,在搅拌过程中滴加80mmol碘甲烷,加热回流48h,冷却至室温后,过滤,用少量冷乙醚洗涤三次,烘干,得到橙黄色沉淀7.8g(产率87%)。
(5)1,2-二(吡啶-4-基)乙烯的制备
将4-甲基吡啶(4.684g,50.3mmol)、4-吡啶甲醛(5.392g,50.4mmol)和醋酸酐(5.202g,51.0mmol)依次加入100mL三口瓶中,混合物在120℃下搅拌3h,冷却到室温,用2mol/L Na2SO4溶液洗涤三次,再用1mol/LNaOH溶液中和,过滤,用乙醇/水重结晶,固体烘干得到1,2-二(吡啶-4-基)乙烯(3.8g,产率约42%)。
(6)三嗪三咪唑的制备
将咪唑(IM)(2.04g,0.03mol),三乙胺(TEA)(3.03g,0.03mol)和四氢呋喃(THF)(100ml)引入装有水的250ml三颈圆底玻璃烧瓶中(机械搅拌器,回流冷凝器,干燥氮气入口)。将混合物在氮气氛下加热至50℃,并搅拌直至咪唑完全溶解。在1小时后加入溶解在50ml THF中的三聚氯氰(1.845g,0.01mol),然后,将混合物进一步加热至75℃并搅拌2h。然后将混合物蒸馏除去THF,将粗产物用去离子水洗涤3次,然后在60℃下真空干燥10h。产率:73%。
(7)三-(甲基咪唑)-三嗪的制备
将2-甲基咪唑(2MI)(2.46g,0.03mol),TEA(3.03g,0.03mol)和THF(100ml)引入装有机械搅拌器的250ml三颈圆底玻璃烧瓶中(机械搅拌器,回流冷凝器,干燥氮气入口)。将混合物在氮气氛下加热至50℃,并搅拌直至2MI完全溶解。在1小时后加入溶解在50ml THF中的三聚氯氰(1.845g,0.01mol),然后,将混合物进一步加热至75℃并搅拌4h。然后将混合物蒸馏除去THF,将粗产物用去离子水洗涤3次,然后在60℃下真空干燥10h。产率:80%。
(8)2,2联吡啶、4,4联吡啶、邻菲罗啉等均为现成药品。
实施例2
将实施例1中制备的0.624g(2mmol)的2,4,6-三(吡啶-4-基)-1,3,5-三嗪加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至0,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.563g(3mmol)Na2B12H12的50mL水溶液添加至溶液A中,迅速生成浅黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物BOFs-TPT-H。所得目标产物变色的激发波长阈值大致位于460nm到520nm之间,光响应时间为3s,自由基寿命在常温下为永久,升高到80℃自由基消失。
实施例3
将实施例1中制备的0.624g(2mmol)的2,4,6-三(吡啶-3-基)-1,3,5-三嗪加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至0,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.563g(3mmol)Na2B12H12的50mL水溶液添加至溶液A中,迅速生成浅黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于460nm到520nm之间,光响应时间为10s,自由基寿命在常温下为永久,升高到80℃自由基消失。
实施例4
将实施例1中制备的0.624g(2mmol)的2,4,6-三(吡啶-2-基)-1,3,5-三嗪加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至0,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.563g(3mmol)Na2B12H12的50mL水溶液添加至溶液A中,迅速生成浅黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于460nm到520nm之间,光响应时间为20s,自由基寿命在常温下为永久,升高到80℃自由基消失。
实施例5
将实施例1中制备的0.3858g(1.5mmol)的甲基紫精加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至7,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有1.223g(3mmol)Cs2B12H12的50mL水溶液添加至溶液A中,迅速生成浅黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于360nm到420nm之间,光响应时间为60s,自由基寿命在常温下为4h,升高到100℃自由基消失。
实施例6
将实施例1中制备的0.2733g(1.5mmol)的1,2-二(吡啶-4-基)乙烯加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至2,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.659g(3mmol)K2B12H12的50mL水溶液添加至溶液A中,迅速生成黄褐色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于400nm到460nm之间,光响应时间为30s,自由基寿命在常温下为3h,升高到110℃自由基消失。
实施例7
将实施例1中制备的0.846g(3mmol)的三嗪三咪唑加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至0,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.563g(3mmol)Na2B12H12的50mL水溶液添加至溶液A中,迅速生成淡黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于520nm到580nm之间,光响应时间为120s,自由基寿命在常温下为2h,升高到110℃自由基消失。
实施例8
将实施例1中制备的0.981g(3mmol)的三嗪三咪唑加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至0,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.563g(3mmol)Na2B12H12的50mL水溶液添加至溶液A中,迅速生成淡黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于400nm到460nm之间,光响应时间为180s,自由基寿命在常温下为6h,升高到100℃自由基消失。
实施例9
将实施例1中提到的0.3124g(2mmol)的2,2-联吡啶加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至5,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.8152g(2mmol)Cs2B12H12的50mL水溶液添加至溶液A中,迅速生成淡红色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于360nm到420nm之间,光响应时间为240s,自由基寿命在常温下为5h,升高到130℃自由基消失。
实施例10
将实施例1中提到的0.3124g(2mmol)的4,4-联吡啶加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至3,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.8152g(2mmol)Cs2B12H12的50mL水溶液添加至溶液A中,迅速生成淡黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于400nm到460nm之间,光响应时间为180s,自由基寿命在常温下为3h,升高到120℃自由基消失。
实施例11
将实施例1中提到的0.1982g(1mmol)的邻菲罗啉加入含有100mL超纯水的250mL圆底烧瓶中,然后用稀盐酸将pH调节至3,并在室温(25℃)下超声搅拌直至溶液完全澄清透明,得到溶液A;将含有0.8152g(2mmol)Cs2B12H12的50mL水溶液添加至溶液A中,迅速生成淡黄色沉淀,继续搅拌30分钟,过滤获得沉淀物,分别用少量的水和乙醇洗涤3次。通过真空干燥获得目标产物。所得目标产物变色的激发波长阈值大致位于400nm到460nm之间,光响应时间为240s,自由基寿命在常温下为4h,升高到90℃自由基消失。
实施例12
分别将实施例2~11中的硼簇换成阴离子为1-氟十一氢十二硼烷([B12H11F]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为3~3600s,自由基寿命在常温下为1h~永久,升高到50~150℃自由基消失。
实施例13
分别将实施例2~11中的硼簇换成阴离子为1-氯十一氢十二硼烷([B12H11Cl]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为20~3000s,自由基寿命在常温下为1h~永久,升高到40~150℃自由基消失。
实施例14
分别将实施例2~11中的硼簇换成阴离子为1-溴十一氢十二硼烷([B12H11Br]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为10~1000s,自由基寿命在常温下为1h~永久,升高到60~150℃自由基消失。
实施例15
分别将实施例2~11中的硼簇换成阴离子为1-碘十一氢十二硼烷([B12H11I]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到500nm之间,光响应时间为30~2000s,自由基寿命在常温下为1h~永久,升高到50~150℃自由基消失。
实施例16
分别将实施例2~11中的硼簇换成阴离子为1-氨基十一氢十二硼烷([B12H11NH3]-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到700nm之间,光响应时间为20~1500s,自由基寿命在常温下为1h~永久,升高到30~150℃自由基消失。
实施例17
分别将实施例2~11中的硼簇换成阴离子为1-羟基十一氢十二硼烷([B12H11OH]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到500nm之间,光响应时间为10~2500s,自由基寿命在常温下为1h~永久,升高到50~150℃自由基消失。
实施例18
分别将实施例2~11中的硼簇换成阴离子为十二氟十二硼烷([B12F12]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到400nm之间,光响应时间为30~1000s,自由基寿命在常温下为1h~永久,升高到30~150℃自由基消失。
实施例19
分别将实施例2~11中的硼簇换成阴离子为十二氯十二硼烷([B12Cl12]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到500nm之间,光响应时间为20~2500s,自由基寿命在常温下为1h~永久,升高到50~150℃自由基消失。
实施例20
分别将实施例2~11中的硼簇换成阴离子为十二溴十二硼烷([B12Br12]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为40~2000s,自由基寿命在常温下为1h~永久,升高到40~150℃自由基消失。
实施例21
分别将实施例2~11中的硼簇换成阴离子为十二碘十二硼烷([B12I12]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为40~2500s,自由基寿命在常温下为1h~永久,升高到40~150℃自由基消失。
实施例22
分别将实施例2~11中的硼簇换成阴离子为十二羟基十二硼烷([B12(OH)12]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到600nm之间,光响应时间为30~2000s,自由基寿命在常温下为1h~永久,升高到60~150℃自由基消失。
实施例23
分别将实施例2~11中的硼簇换成阴离子为十氢十硼烷([B10H10]2-)的硼簇,其他操作均与实施例2~11中相同。所得目标产物变色的激发波长阈值大致位于200nm到550nm之间,光响应时间为20~2000s,自由基寿命在常温下为1h~永久,升高到40~150℃自由基消失。
Claims (4)
1.一种基于硼簇阴离子光致变色材料的制备方法,其特征在于包括以下步骤:
将共轭性多吡啶分子加入超纯水中,然后用无机酸将pH调节至-1~7,并在室温下超声搅拌直至溶液完全澄清透明,得到溶液A;
将含有硼簇化合物的水溶液加入溶液A中,生成沉淀后继续搅拌0.5~24h,过滤获得沉淀物,洗涤、真空干燥得到基于硼簇阴离子的光致变色材料;
其中,所述共轭性多吡啶分子为2,4,6-三(吡啶-4-基)-1,3,5-三嗪、2,4,6-三(吡啶-3-基)-1,3,5-三嗪、2,4,6-三(吡啶-2-基)-1,3,5-三嗪、甲基紫精、1,2-二(吡啶-4-基)乙烯、2,2-联吡啶、4,4-联吡啶、邻菲罗啉中的一种;
所述硼簇化合物的阳离子为钠、钾、铯中的一种;阴离子为[B12H11F]2-、[B12H11Cl]2-、[B12H11Br]2-、[B12H11I]2-、[B12H11NH3]-、[B12H11OH]2-、[B12F12]2-、[B12Cl12]2-、[B12Br12]2-、[B12I12]2-、[B12(OH)12]2-、[B12H12]2-、[B10H10]2-中的一种。
2.如权利要求1所述基于硼簇阴离子光致变色材料的制备方法,其特征在于所得溶液A的浓度为0.01~150mmol/L。
3.如权利要求1所述基于硼簇阴离子光致变色材料的制备方法,其特征在于硼簇化合物与共轭性多吡啶分子的摩尔比为1:(0.01~100)。
4.如权利要求1所述基于硼簇阴离子光致变色材料的制备方法,其特征在于所述无机酸为盐酸、硫酸、磷酸中的一种。
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Non-Patent Citations (5)
Title |
---|
An inorganic-organic hybrid framework from the assembly of an electron-rich diphosphonate and electron-deficient tripyridyl moiety;Ma Yu-Juan;《JOURNAL OF MATERIALS CHEMISTRY C》;20180921;全文 * |
Inductive effects of 10 and 12-vertex closo-carborane anions: cluster size and charge make a difference;Estrada Jess等;《CHEMICAL COMMUNICATIONS》;20151207;全文 * |
Photochromic Hybrid Containing In Situ-Generated Benzyl Viologen and Novel Trinuclear [Bi3Cl14](5-): Improved Photoresponsive Behavior by the pi center dot center dot center dot pi Interactions and Size Effect of Inorganic Oligomer;Lin Rong-Guang等;《INORGANIC CHEMISTRY》;20140602;全文 * |
基于碳硼烷阴离子[CB_(11)H_(12)]~-的一价铜配合物的合成及性质研究;张康;《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》;20190815;全文 * |
电子迁移型光色—荧光多功能超分子体系的构建与性能表征;陈恒隽;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20160115;全文 * |
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