CN112010854B - Trnano-ger's alkali derivative, preparation method thereof and test method for mechanical-induced fluorescence enhancement characteristics - Google Patents
Trnano-ger's alkali derivative, preparation method thereof and test method for mechanical-induced fluorescence enhancement characteristics Download PDFInfo
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- 239000003513 alkali Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010998 test method Methods 0.000 title claims abstract description 9
- 239000002585 base Substances 0.000 claims abstract description 74
- 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 claims abstract description 70
- 238000003958 fumigation Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- 238000012360 testing method Methods 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 35
- LLLMDRXIQZOTJE-UHFFFAOYSA-N 1,5-diazocine Chemical compound C1=CN=CC=CN=C1 LLLMDRXIQZOTJE-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 26
- 239000012046 mixed solvent Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000004440 column chromatography Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- XIPGCKFASRXQSN-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[4-(1,2,2-triphenylethenyl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C(=C(C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 XIPGCKFASRXQSN-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 13
- 235000011009 potassium phosphates Nutrition 0.000 claims description 13
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 12
- -1 1,2, 2-triphenylethenyl Chemical group 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- YZTFIKANQHTFDZ-UHFFFAOYSA-N diazocine Chemical compound C1=CC=CN=NC=C1 YZTFIKANQHTFDZ-UHFFFAOYSA-N 0.000 claims description 5
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 11
- 230000009471 action Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000002189 fluorescence spectrum Methods 0.000 description 31
- 239000007787 solid Substances 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 238000000605 extraction Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000002274 desiccant Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000003480 eluent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 238000007698 E/Z-isomerization reaction Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XSIVQWOJIOHPIZ-UHFFFAOYSA-N [4-(1,2,2-triphenylethenyl)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 XSIVQWOJIOHPIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009509 drug development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
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- 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
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- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- 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
- G01N2021/6417—Spectrofluorimetric devices
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Abstract
The invention relates to the technical field of organic photoelectric functional materials, and provides a preparation method of a high-performance organic photoelectric functional material
A base derivative, a preparation method thereof and a test method of the mechanical induced fluorescence enhancement characteristic. The invention provides a tetraphenylethylene modified
The alkali derivative has a structural formula shown in formula I, has aggregation-induced emission performance and mechanical-induced fluorescence enhancement characteristics, has obvious fluorescence intensity change under the action of mechanical force, does not generate crystal form transformation, and has good fumigation recovery characteristics and stability. The preparation method provided by the invention is simple to operate and mild in reaction conditions. The invention provides a tetraphenylethylene modified
The method for enhancing the fluorescence by mechanically inducing the alkali derivative has simple steps and can modify tetraphenylethylene under the action of mechanical pressure
The fluorescence intensity change, fumigation recovery performance, crystal form change and stability of the alkali derivative are tested.
Description
Technical Field
The invention relates to the technical field of organic photoelectric functional materials, in particular to a composite material
A base derivative, a preparation method thereof and a test method of the mechanical induced fluorescence enhancement characteristic.
Background
Since the first discovery of the aggregation-induced emission (AIE) phenomenon in the early century, a series of mechanism explanations have been gradually proposed, including distorted intramolecular charge transfer (TICT), limitation of E/Z isomerization, photoinduced intramolecular proton transfer (ESIPT), molecular co-planarity, and J-mer formation, etc. These theories are applicable only to the interpretation of the luminescence of a small fraction of the AIE molecules and not to the whole. The mechanisms of Intramolecular rotation Restriction (RIR) and Intramolecular vibration Restriction (RIV) are widely applicable, and the two mechanisms are respectively applicable to explaining the AIE luminescence phenomenon of two types of molecules and almost cover the whole AIE molecular system. Subsequently, in 2014, the Down loyalty academy has further merged and unified the two mechanisms, proposed a mechanism of intramolecular motion Restriction (RIM) and generally accepted by researchers.
Disclosure of Invention
In view of the above, the present invention provides a method for producing
A base derivative, a preparation method thereof and a test method of the mechanical induced fluorescence enhancement characteristic. The invention provides a tetraphenylethylene modified
The alkali derivative has the characteristics of aggregation-induced emission performance and mechanical induced fluorescence enhancement, is a novel multifunctional AIE molecule, and has a simple preparation method.
In order to achieve the above object, the present invention provides the following technical solutions:
tetraphenylethylene modified
The alkali derivative has a structural formula shown in formula I:
the invention provides the tetraphenylethylene modified
A process for the preparation of a base derivative comprising the steps of:
under the protection atmosphere, 4- (1,2, 2-triphenylethenyl) phenylboronic acid pinacol ester, 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f)][1,5]Diazocine, phosphate, catalyst and solvent are mixed for Suzuki coupling reaction to obtain tetraphenylethylene modified
A base derivative.
Preferably, the molar ratio of the 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine to the 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester is 1 (2-3).
Preferably, the catalyst is one or more of tetratriphenylphosphine palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bis (triphenylphosphine) palladium dichloride; the dosage of the catalyst is 1-5% of the mass of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine.
Preferably, the phosphate is potassium phosphate and/or sodium phosphate.
Preferably, the temperature of the Suzuki coupling reaction is 80-120 ℃, and the time is 15-30 h.
Preferably, the solvent is an organic solvent or an organic solvent-water mixed solvent; the mass fraction of water in the organic solvent-water mixed solvent is 5-30%.
Preferably, after the Suzuki coupling reaction is completed, the method further comprises post-treating the obtained product liquid, wherein the post-treating comprises the following steps: cooling the obtained product liquid to room temperature, and sequentially concentrating, extracting, performing column chromatography and drying to obtain tetraphenylethylene modified product
A base derivative.
The invention also provides a tetraphenylethylene modified
The method for testing the fluorescence enhancement property induced by the base derivative mechanically comprises the following steps:
(1) modified by tetraphenylethylene as described in the above scheme
The base derivative being treated under pressure to modify tetraphenylethylene before and after the treatment under pressure
Carrying out fluorescence intensity test on the alkali derivative; the method of the pressure treatment includes grinding or pressurizing using a tablet press;
(2) for tetraphenylethylene modified after pressure treatment in (1)
Solvent fumigation of base derivatives, modification of tetraphenylethylene by solvent fumigation
The fluorescence intensity of the base derivative is tested;
(3) for tetraphenylethylene modified after pressure treatment in (1)
Subjecting the base derivative to a powder X-ray diffraction test;
(4) for tetraphenylethylene modified after pressure treatment in (1)
By heat treatment of alkali derivatives, modified by tetraphenylethylene after heat treatment
Carrying out fluorescence intensity test on the alkali derivative;
the steps (2), (3) and (4) have no requirement on time sequence.
Preferably, the milling is tetraphenylethylene modified
The alkali derivative is placed between two glass sheets and then manually ground; the pressure for pressurizing by using the tablet press is 3-30 MPa;
the solvent used for solvent fumigation is one or more of dichloromethane, trichloromethane, ethanol, methanol and tetrahydrofuran;
the temperature of the heat treatment is 100-120 ℃, and the time is 10-60 min.
The invention provides a tetraphenylethylene modified
The structural formula of the alkali derivative is shown as formula I, and the tetraphenylethylene modified alkali derivative is modified by tetraphenylethylene
Among the alkali derivatives, the alkali derivatives are,
the basic structural element is a V-shaped structure, can prevent pi-pi tight stacking among molecules, and has chiral structural elements, N-dialkyl in the structure is a typical electron-pushing structure,
the base is directly linked to tetraphenylethylene via a carbon-carbon single bond, providing the molecule with rotational freedom. The invention provides a tetraphenylethylene modified
The alkali derivative has aggregation-induced emission performance and mechanical-induced fluorescence enhancement property, the fluorescence intensity is obviously changed under the action of mechanical force, and crystal form transformation cannot occur, and the tetraphenylethylene modified alkali derivative provided by the invention
The alkali derivative also has better fumigation recovery property and thermal stability.The results of the examples show that tetraphenylethylene is modified after being subjected to mechanical stress
The fluorescence intensity of the alkali derivative is obviously increased, the fluorescence intensity and the wavelength of the alkali derivative can be recovered through solvent rotary evaporation, and the alkali derivative is modified by tetraphenylethylene under the condition of heat treatment
The fluorescence intensity of the alkali derivative does not change obviously, which shows that the alkali derivative has excellent stability.
The invention also provides the tetraphenylethylene modified by the scheme
The preparation method of the alkali derivative provided by the invention is simple to operate and mild in reaction conditions.
The invention also provides a tetraphenylethylene modified
The method for testing the fluorescence enhancement property induced by the mechanical of the alkali derivative does not exist in the field at present
The invention also provides a test method for the mechanical induced fluorescence enhancement property of the alkali derivative, which has simple steps and can modify tetraphenylethylene under the action of mechanical pressure
The fluorescence intensity change, fumigation recovery performance, crystal form change and stability of the alkali derivative are tested.
Drawings
FIG. 1 shows the structure of formula I prepared in example 1
High resolution of base derivativesA spectrogram;
FIG. 2 shows the structure of formula I prepared in example 1
An infrared absorption spectrum of the base derivative;
FIG. 3 shows the structure of formula I prepared in example 1
Nuclear magnetic resonance hydrogen spectra of base derivatives;
FIG. 4 shows the structure of formula I prepared in example 1
Nuclear magnetic resonance carbon spectrum of the base derivative;
FIG. 5 shows the structure of formula I in example 6
AIE performance plots for base derivatives;
FIG. 6 shows the structure of formula I in example 11
The original shape of the alkali derivative and a fluorescence spectrogram after the mechanical force and the solvent fumigation;
FIG. 7 shows the structure of formula I in example 11
The change relation curve of the maximum emission wavelength and the fluorescence emission intensity of the alkali derivative after the action of mechanical force and the solvent fumigation;
FIG. 8 shows the structure of formula I in example 14
Fluorescence emission spectrograms of the base derivatives under the action of different mechanical forces;
FIG. 9 shows the structure of formula I in example 14
The change relation curve of the fluorescence emission intensity of the alkali derivative along with the pressure after the alkali derivative acts on different mechanical forces;
FIG. 10 shows the structure of formula I in example 14
Powder diffraction patterns of the alkali derivative after the action of different mechanical forces;
FIG. 11 shows the structure of formula I after pressure treatment in example 15
A fluorescence emission spectrogram of the alkali derivative after heat treatment;
FIG. 12 shows the structure of formula I after pressure treatment in example 15
The fluorescence emission intensity of the base derivative as a function of the heat treatment time.
Detailed Description
The invention provides a tetraphenylethylene modified
The alkali derivative has a structural formula shown in formula I:
in the present invention, the structure of formula I is tetraphenylethylene modified
The chemical name of the base derivative is: 2, 8-bis [4- (1,2, 2-triphenylethenyl) phenyl]-6H,12H-5, 11-methylenediphenyl [ b, f ]][1,5]Diazocine.
The invention also provides the tetraphenylethylene modified by the scheme
A process for the preparation of a base derivative comprising the steps of:
under the protection atmosphere, 4- (1,2, 2-triphenylethenyl) phenylboronic acid pinacol ester, 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f)][1,5]Diazocine, phosphate, catalyst and solvent are mixed for Suzuki coupling reaction to obtain tetraphenylethylene modified
A base derivative.
In the invention, the protective atmosphere is preferably inert gas, and particularly preferably high-purity nitrogen, common nitrogen or argon; the molar ratio of the 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine to the 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester is preferably 1 (2-3), and more preferably 1 (2.3-2.5); the sources of the 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine and 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester are not particularly limited in the present invention, and they may be commercially available or synthesized according to a method well known to those skilled in the art.
In the present invention, the phosphate is preferably sodium phosphate and/or potassium phosphate; the molar ratio of the 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine to phosphate is preferably 1 (2-3.5); the phosphate provides an alkaline environment for the Suzuki coupling reaction.
In the present invention, the catalyst is preferably palladium tetratriphenylphosphine (Pd (Ph)3P)4) [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (PdCl)2(dppf)) and bis (triphenylphosphine) palladium dichloride ((pph)3)2PdCl2) One or more of the above; the catalyst is preferably used in an amount of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f][1,5]1 to 5 percent, more preferably 2 to 3 percent of the mass of diazocine.
In the present invention, the solvent is preferably an organic solvent or an organic solvent-water mixed solvent; the mass fraction of water in the organic solvent-water mixed solvent is preferably 5-30%, and more preferably 10-25%; the organic solvent is preferably one or more of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dioxane and cyclohexanone; the organic solvent in the organic solvent-water mixed solvent is preferably one or more of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, dioxane and cyclohexanone.
In the embodiment of the present invention, it is preferable that the pinacol ester of 4- (1,2, 2-triphenylvinyl) phenylboronic acid, 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine and the phosphate are dissolved in the solvent, and then the catalyst is added.
In the invention, the temperature of the Suzuki coupling reaction is preferably 80-120 ℃, more preferably 90-110 ℃, and the reaction time is preferably 15-30 h, more preferably 20-25 h; the Suzuki coupling reaction is preferably carried out under the conditions of oil bath and reflux; the reaction formula of the Suzuki coupling reaction is shown as formula II:
after the Suzuki coupling reaction is finished, the invention preferably carries out post-treatment on the obtained product liquid. In the present invention, the post-treatment preferably comprises the steps of:
cooling the obtained product liquid to room temperature, and sequentially concentrating, extracting, performing column chromatography and drying to obtain tetraphenylethylene modified product
A base derivative.
In the present invention, the concentration method is preferably rotary evaporation, and the present invention preferably concentrates the obtained product feed liquid to 1/3 of the original volume.
In the present invention, the extraction is preferably carried out on the obtained concentrated solution; the extractant for extraction is preferably a mixed solution of dichloromethane and saturated saline solution; the volume ratio of the dichloromethane to the saturated saline solution is preferably 1: 2; the extraction times are preferably 3 times, and organic phases obtained by the 3 times of extraction are combined; after the organic phase is obtained, the organic phase is preferably dried by using anhydrous sodium sulfate, and the using ratio of the extract to the anhydrous sodium sulfate is preferably 100mL:2 g; the drying time is preferably 8-12 h; after drying, the present invention preferably removes the drying agent (anhydrous sodium sulfate) by filtration, and then removes the organic solvent from the filtrate by rotary evaporation to obtain a solid product, which is subjected to column chromatography.
In the invention, the column chromatography is to carry out silica gel column chromatography separation on the obtained solid product; the eluent for column chromatography is preferably a mixed solvent of dichloromethane and petroleum ether, the volume ratio of dichloromethane to petroleum ether in the mixed solvent is preferably 1:1, and the boiling point of petroleum ether is preferably 60-90 ℃.
In the invention, the drying is specifically drying the product obtained by column chromatography; the drying agent is preferably anhydrous sodium sulfate and/or anhydrous magnesium sulfate.
The invention also provides a tetraphenylethylene modified
The method for testing the fluorescence enhancement property induced by the base derivative mechanically comprises the following steps:
(1) modified by tetraphenylethylene as described in the above scheme
The base derivative being treated under pressure to modify tetraphenylethylene before and after the treatment under pressure
Carrying out fluorescence intensity test on the alkali derivative; the method of the pressure treatment includes grinding or pressurizing using a tablet press;
(2) for tetraphenylethylene modified after pressure treatment in (1)
Fumigating the solvent with alkali derivativeModified by tetraphenylethylene after fumigant
The fluorescence intensity of the base derivative is tested;
(3) for tetraphenylethylene modified after pressure treatment in (1)
Subjecting the base derivative to a powder X-ray diffraction test;
(4) for tetraphenylethylene modified after pressure treatment in (1)
By heat treatment of alkali derivatives, modified by tetraphenylethylene after heat treatment
Carrying out fluorescence intensity test on the alkali derivative;
the steps (2), (3) and (4) have no requirement on time sequence.
The invention is modified by tetraphenylethylene
The base derivative being treated under pressure to modify tetraphenylethylene before and after the treatment under pressure
Carrying out fluorescence intensity test on the alkali derivative; the method of the pressurization treatment includes grinding or pressurization using a tablet press. In the present invention, the grinding is preferably tetraphenylethylene-modified
The alkali derivative is placed between two glass sheets and then manually ground; the pressure for pressurizing by using the tablet press is preferably 3-30 MPa, and more preferably 5-25 MPa; the fluorescence intensity test is specifically used for testing tetraphenylethylene modification before and after pressurization treatment
Fluorescence spectra of base derivatives; the result of the fluorescence spectrum test can be used for obtaining the tetraphenylethylene modified after the pressurization treatment
How the fluorescence intensity of the base derivative changes. In a particular embodiment of the invention, the tetraphenylethylene is modified after pressure treatment
The fluorescence intensity of the base derivative was significantly increased.
The invention modifies tetraphenylethylene after pressure treatment in (1)
Solvent fumigation of base derivatives, modification of tetraphenylethylene by solvent fumigation
The fluorescence intensity of the base derivative is tested; the method of the fluorescence intensity test is the same as that in (1). In the invention, the solvent used for solvent fumigation is preferably one or more of dichloromethane, trichloromethane, ethanol, methanol and tetrahydrofuran; the time for fumigating the solvent is preferably 10 min. The invention tests tetraphenylethylene modified after solvent fumigation
The fluorescence spectrum of the alkali derivative can determine the fumigation resilience; in a specific embodiment of the invention, the solvent is fumigated followed by tetraphenylethylene modification
The alkali derivative has recovery phenomenon in both wavelength and fluorescence intensity.
The invention modifies tetraphenylethylene after pressure treatment in (1)
The base derivatives were subjected to powder X-ray diffraction testing. The method for powder X-ray diffraction test of the invention has no special requirements, and the powder X-ray diffraction test method well known to the technical personnel in the field can be used. Whether the pressure treatment can modify the tetraphenylethylene can be known through the powder X-ray diffraction test result
The crystal form of the base derivative is changed; in a particular embodiment of the invention, powder X-ray diffraction test results show that tetraphenylethylene-modified after pressure treatment
The crystal form of the alkali derivative can not be changed, the phenomenon is completely different from the prior traditional AIE molecule with mechanical induced fluorescence discoloration, and the characteristic ensures that the AIE molecule provided by the invention
Base derivatives are more advantageous in fluorescence detection because the human eye is often more sensitive to fluorescence enhancement than to fluorescence quenching (attenuation), using the invention
The alkali derivative can be visible to naked eyes when being subjected to fluorescence detection, and can be used for detecting micro cracks.
The invention modifies tetraphenylethylene after pressure treatment in (1)
By heat treatment of alkali derivatives, modified by tetraphenylethylene after heat treatment
The base derivative was subjected to fluorescence intensity measurement. In the invention, the temperature of the heat treatment is preferably 100-120 ℃, more preferably 110 ℃, and the time is preferably 10-60 min; the method for measuring the fluorescence intensity and the methodThe cases are consistent; the invention modifies tetraphenylethylene after heat treatment
The alkali derivative is subjected to fluorescence intensity test, and the stability of the alkali derivative can be judged according to the fluorescence intensity test result. In a particular embodiment of the invention, the tetraphenylethylene-modified after the heat treatment
The fluorescence intensity of the base derivative and no significant change before heat treatment indicate that the tetraphenylethylene modified compounds provided by the present invention
The alkali derivative has good stability.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Tetraphenylethylene modified with the structure of formula I
Synthesis of base derivative 1
The synthesis steps are as follows:
under the protection of high-purity nitrogen, 124mg of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, 300mg of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester and 171mg of potassium phosphate (the molar ratio of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, the molar ratio of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester to potassium phosphate is 1:2:2.5) are mixed, dissolved in a mixed solvent prepared by 80mL of tetrahydrofuran and 20mL of water (the volume ratio of tetrahydrofuran to water is 4:1), 5.0mg of a tetrakistriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetrakistriphenylphosphine palladium catalyst is 2, 2.0 percent of 8-dibromo-6H, 12H-5, 11-methylene diphenyl [ b, f ] [1,5] diazocine in mass is refluxed for 15 hours under the condition of oil bath at 100 ℃.
After the reaction was complete, the oil bath was removed, the system was allowed to cool to room temperature naturally, a portion of the organic solvent was removed by a rotary evaporator, and the mixture was concentrated to 1/3 in its original volume. Then extracting the system with 60mL of mixed solvent of dichloromethane and saturated salt water in a volume ratio of 1:2 for three times, collecting an organic phase, removing water from the organic phase with anhydrous sodium sulfate, wherein the dosage of the anhydrous sodium sulfate is determined according to the volume of the extract, 2g of anhydrous sodium sulfate is added into each 100mL of the extract, standing for 12 hours, filtering at normal pressure, removing water-absorbing drying agent anhydrous sodium sulfate, and removing organic solvents of dichloromethane and tetrahydrofuran on a rotary evaporator; and (3) carrying out column chromatography separation on the obtained residual solid, wherein an eluent used for the column chromatography separation is a mixed solvent of petroleum ether (with a boiling point of 60-90 ℃) and dichloromethane in a volume ratio of 1:1, and finally obtaining a compound: 2, 8-bis [4- (1,2, 2-triphenylvinyl) phenyl ] -6H,12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine in 69.3% yield. Identifying the chemical structure of the product by using a high-resolution mass spectrum, an infrared absorption spectrum, a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum; the obtained high-resolution mass spectrum is shown in FIG. 1, the infrared absorption spectrum is shown in FIG. 2, the nuclear magnetic resonance hydrogen spectrum is shown in FIG. 3, and the nuclear magnetic resonance carbon spectrum is shown in FIG. 4. As can be seen from FIGS. 1 to 4, the obtained product conforms to the structure shown in formula I.
Example 2
Structure of formula I
Synthesis of base derivative 2
The synthesis steps are as follows:
under the protection of high-purity nitrogen, 124mg of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, 450mg of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester and 171mg of potassium phosphate (the molar ratio of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine and the molar ratio of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester to potassium phosphate is 1:3:2.5) are mixed, dissolved in a mixed solvent prepared by 80mL of dioxane and 20mL of water (the volume ratio of dioxane to water is 4:1), 7.5mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the tetratriphenylphosphine palladium catalyst is used in an amount of 2, 3.0 percent of 8-dibromo-6H, 12H-5, 11-methylene diphenyl [ b, f ] [1,5] diazocine in mass is refluxed for 15 hours in an oil bath at the temperature of 120 ℃.
After the reaction was complete, the oil bath was removed, the system was allowed to cool naturally to room temperature, and a portion of the organic solvent was removed by a rotary evaporator, and the mixture was concentrated to 1/3 in its original volume. Then, 60mL of a mixed solvent of dichloromethane and saturated brine in a volume ratio of 1:2 is used for extracting the system for three times, the organic phase is collected and subjected to dehydration treatment by using anhydrous sodium sulfate, the using amount of the anhydrous sodium sulfate is determined according to the volume of the extraction liquid, 2g of anhydrous sodium sulfate is added into each 100mL of the extraction liquid, and the mixture is kept stand for 12 hours. Filtering at normal pressure, removing water-absorbing desiccant anhydrous sodium sulfate, and removing organic solvents such as dichloromethane and dioxane on a rotary evaporator; and (3) carrying out column chromatography separation on the obtained residual solid, wherein the eluent used for the column chromatography separation is a eluent with the volume ratio of 1:1 (the boiling point is 60-90 ℃) and dichloromethane to finally obtain a compound: 2, 8-bis [4- (1,2, 2-triphenylvinyl) phenyl ] -6H,12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine in 76.6% yield. The chemical structure of the product is identified by high resolution mass spectrum, infrared absorption spectrum, nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum, and the result shows that the obtained product conforms to the structure shown in formula I.
Example 3
Structure of formula I
Synthesis of base derivatives 3
The synthesis steps are as follows:
under the protection of high-purity nitrogen, 124mg of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, 450mg of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester and 206mg of potassium phosphate (the molar ratio of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine and the molar ratio of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester to potassium phosphate is 1:3:3) are mixed and dissolved in a mixed solvent prepared by 80mL of dimethyl sulfoxide and 20mL of water (the volume ratio of dimethyl sulfoxide to water is 4:1), 7.5mg of a tetrakistriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetrakistriphenylphosphine palladium catalyst is 2, 3.0 percent of 8-dibromo-6H, 12H-5, 11-methylene diphenyl [ b, f ] [1,5] diazocine in mass is refluxed for 20 hours in an oil bath at the temperature of 80 ℃.
After the reaction is finished, the oil bath is removed, and the system is naturally cooled to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. Then, 60mL of a mixed solution of dichloromethane and saturated brine in a volume ratio of 1:2 was used to extract the system, the extraction was carried out three times, the organic phase was collected and subjected to water removal treatment with anhydrous sodium sulfate, the amount of the drying agent was determined according to the volume of the extract, 2g of anhydrous sodium sulfate was added to each 100mL of the extract, and the mixture was allowed to stand for 12 hours. Filtering at normal pressure to remove the anhydrous sodium sulfate of the water-absorbing drying agent, and removing the organic solvents of dichloromethane and dimethyl sulfoxide on a rotary evaporator; and (3) carrying out column chromatography separation on the obtained residual solid, wherein an eluent used for the column chromatography separation is a mixed solvent of petroleum ether (with a boiling point of 60-90 ℃) and dichloromethane in a volume ratio of 1:1, and finally obtaining a compound: 2, 8-bis [4- (1,2, 2-triphenylvinyl) phenyl ] -6H,12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine in 58.3% yield. The chemical structure of the product is identified by high resolution mass spectrum, infrared absorption spectrum, nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum, and the result shows that the obtained product conforms to the structure shown in formula I.
Example 4
Structure of formula I
Synthesis of base derivative 4
The synthesis steps are as follows:
under the protection of high-purity nitrogen, 124mg of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, 300mg of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester and 206mg of potassium phosphate (the molar ratio of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, the molar ratio of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester to potassium phosphate is 1:2.5:3) are mixed and dissolved in a mixed solvent prepared by 80mL of dioxane and 20mL of water (the volume ratio of dioxane to water is 4:1), 10.0mg of tetratriphenylphosphine palladium catalyst is added after complete dissolution, the tetratriphenylphosphine palladium catalyst is used in an amount of 2, 4.0 percent of 8-dibromo-6H, 12H-5, 11-methylene diphenyl [ b, f ] [1,5] diazocine in mass is refluxed for 30 hours in 110 ℃ oil bath.
After the reaction is finished, the oil bath is removed, and the system is naturally cooled to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. Then, 60mL of a mixed solvent of dichloromethane and saturated brine in a volume ratio of 1:2 is used for extracting the system for three times, the organic phase is collected and subjected to water removal treatment by using anhydrous sodium sulfate, the amount of a drying agent is determined according to the volume of the extraction liquid, 2g of anhydrous sodium sulfate is added into each 100mL of the extraction liquid, and the mixture is kept standing for 12 hours. Filtering at normal pressure, removing water-absorbing desiccant anhydrous sodium sulfate, and removing organic solvents such as dichloromethane and dioxane on a rotary evaporator; and (3) carrying out column chromatography separation on the obtained residual solid, wherein the eluent used for the column chromatography separation is a eluent with the volume ratio of 1:1 (the boiling point is 60-90 ℃) and dichloromethane mixed solvent to finally obtain the compound 2, 8-bis [4- (1,2, 2-triphenylethenyl) phenyl ] -6H,12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine with the yield of 65.5%. The chemical structure of the product is identified by high resolution mass spectrum, infrared absorption spectrum, nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum, and the result shows that the obtained product conforms to the structure shown in formula I.
Example 5
Structure of formula I
Synthesis of base derivatives 5
The synthesis steps are as follows:
under the protection of high-purity nitrogen, 124mg of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, 300mg of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester and 171mg of potassium phosphate (the molar ratio of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine, the molar ratio of 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester to potassium phosphate is 1:2:2.5) are mixed and dissolved in a mixed solvent prepared by 80mL of cyclohexanone and 20mL of water (the volume ratio of cyclohexanone to water is 4:1), 5.0mg of tetrakistriphenylphosphine palladium catalyst is added after complete dissolution, the amount of the tetrakistriphenylphosphine palladium catalyst is 2, 2.0 percent of 8-dibromo-6H, 12H-5, 11-methylene diphenyl [ b, f ] [1,5] diazocine in mass is refluxed for 20 hours in an oil bath at the temperature of 80 ℃.
After the reaction is finished, the oil bath is removed, and the system is naturally cooled to room temperature. A portion of the organic solvent was removed by rotary evaporator and the mixture was concentrated to 1/3. Then, 60mL of a mixed solvent of dichloromethane and saturated brine in a volume ratio of 1:2 is used for extracting the system for three times, the organic phase is collected and subjected to water removal treatment by using anhydrous sodium sulfate, the amount of a drying agent is determined according to the volume of the extraction liquid, 2g of anhydrous sodium sulfate is added into each 100mL of the extraction liquid, and the mixture is kept standing for 12 hours. Filtering at normal pressure, removing water-absorbing desiccant anhydrous sodium sulfate, and removing organic solvents such as dichloromethane and cyclohexanone on a rotary evaporator; and (3) carrying out column chromatography separation on the obtained residual solid, wherein an eluent used for the column chromatography separation is a mixed solvent of petroleum ether (with a boiling point of 60-90 ℃) and dichloromethane in a volume ratio of 1:1, and finally obtaining a compound: 2, 8-bis [4- (1,2, 2-triphenylvinyl) phenyl ] -6H,12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine in 69.3% yield. The chemical structure of the product is identified by high resolution mass spectrum, infrared absorption spectrum, nuclear magnetic resonance hydrogen spectrum and nuclear magnetic resonance carbon spectrum, and the result shows that the obtained product conforms to the structure shown in formula I.
Example 6
Structure of formula I
AIE Performance test 1 of base derivatives
The testing steps are as follows:
structural general formula I
The base derivative is dissolved in tetrahydrofuran and prepared to have a concentration of 1 × 10-4M, mother liquor. Transferring 1mL of mother solution to a 10mL volumetric flask, adding tetrahydrofuran with calculated amount, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing into 1 × 10-5M and a mixed solution having water contents of 0 to 90% respectively, whichThe water content is volume percent.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The instrument was a Perkinelmer LS 55 type fluorescence spectrometer and the measured fluorescence spectra are summarized in FIG. 5. From the spectrum in FIG. 5, it can be seen that the structure shown in formula I
When the water content in the tetrahydrofuran solution of the alkali derivative reaches 70 percent, the structure shown in the formula I
The fluorescence of the base derivative begins to appear, and the fluorescence intensity gradually increases with the increase of the water content, indicating that the compound has AIE performance.
Example 7
Structure of formula I
AIE Performance test 2 of base derivatives
The test procedure was as follows:
will be shown in formula I
The alkali derivative is dissolved in acetonitrile solvent to be prepared into the solution with the concentration of 1 × 10-4M, mother liquor. Transferring 1mL of mother solution to a 10mL volumetric flask, adding acetonitrile with calculated amount, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing the product with the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkin Elmer LS 55 type fluorescence spectrometer. When the structure shown in formula I
When the water content in the acetonitrile solution of the alkali derivative reaches 70 percent, the structure shown in the formula I
The fluorescence of the base derivative begins to appear, and the fluorescence intensity gradually increases with the continuous increase of the water content, indicating that the compound has AIE performance.
Example 8
Structure of formula I
AIE Performance test 3 of base derivatives
The testing steps are as follows:
will have the structure shown in formula I
The alkali derivative is dissolved in dioxane to give a solution with a concentration of 1 × 10-4M, mother liquor. Transferring 1mL of mother solution to a 10mL volumetric flask, adding calculated amount of dioxane, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing into the product with the concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the structure shown in formula I
When the water content of the tetrahydrofuran solution of the alkali derivative reaches 50 percent, the structure shown in the formula I
The onset of fluorescence of the base derivative occurs; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
Example 9
Structure of formula I
AIE Performance test 4 of base derivatives
The testing steps are as follows:
dissolving a compound with a structure shown in formula I in dimethyl sulfoxide to prepare the compound with a concentration of 1 × 10-4M, mother liquor. Transferring 1mL of mother solution to a 10mL volumetric flask, adding calculated amount of dimethyl sulfoxide, dropwise adding deionized water under rapid stirring to constant volume, and finally preparing into 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkin Elmer LS 55 type fluorescence spectrometer. When the structure shown in formula I
When the water content in the dimethyl sulfoxide solution of the alkali derivative reaches 60 percent, the structure shown in the formula I
The onset of fluorescence of the base derivative occurs; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
Example 10
Structure of formula I
AIE Performance test 5 of base derivatives
The testing steps are as follows:
dissolving a compound with a structure shown in formula I in N, N-dimethylformamide to prepare the compound with the concentration of 1 × 10-4M, mother liquor. Transferring 1mL of the mother solution to a 10mL volumetric flask, adding a calculated amount of N, N-dimethylformamide, and stirring rapidlyAdding deionized water dropwise under stirring to desired volume, and making into final product with concentration of 1 × 10-5M and the water content of the mixed solution is 0-90% respectively, and the water content is volume percentage.
And (3) rapidly transferring the solutions to a sample rack of a fluorescence spectrometer for fluorescence spectrum testing, wherein the excitation wavelength is 350nm, and the wavelength of the absorption peak with the lowest energy according to the ultraviolet-visible absorption spectrum of the solutions is selected. The test instrument was a Perkinelmer LS 55 type fluorescence spectrometer. When the structure shown in formula I
When the water content of the N, N-dimethylformamide solution of the alkali derivative reaches 60 percent, the structure shown in the formula I
The onset of fluorescence of the base derivative occurs; the fluorescence intensity gradually increased with the increase of the water content, indicating that the compound has AIE performance.
Example 11
Structure of formula I
Alkali derivative mechanical force response and fumigation recovery test 1
The testing steps are as follows:
structural general formula I
The base derivative was placed in the solid sample cell of a fluorescence spectrometer and its fluorescence spectrum was measured with a PerkinElmer LS 55 type fluorescence spectrometer, the solid sample was taken out and placed between two glass plates, the solid sample was ground by hand and then its fluorescence spectrum was measured with a fluorescence spectrometer. And (3) fumigating the ground solid sample with dichloromethane vapor for 10min, and then testing the fluorescence spectrum of the solid sample by using a fluorescence spectrometer. The grinding and solvent fumigation were repeated 4 times, and the fluorescence spectra were measured after each grinding and solvent fumigation. The resulting fluorescence spectra are summarized in FIG. 6, where FIG. 6 is a structure of formula I
The original shape of the alkali derivative and a fluorescence spectrogram after the mechanical force and the solvent fumigation; the results in FIG. 6 are plotted for the structure of formula I after mechanical force and solvent fumigation
The maximum emission wavelength and fluorescence emission intensity of the base derivative were plotted in FIG. 7.
As can be seen from FIGS. 6 to 7, under the action of mechanical force, the compound represented by formula I
The fluorescence spectrum wavelength of the alkali derivative is only red-shifted by 7nm, and the fluorescence intensity is doubled, as shown in formula I
The base derivatives exhibit significant mechanically induced fluorescence enhancement properties. In the case of dichloromethane fumigation, both fluorescence intensity and wavelength have a reversion phenomenon.
Example 12
Structure of formula I
Alkali derivative mechanical force response and fumigation recovery test 2
The testing steps are as follows:
placing the compound with the structure shown in the formula I in a solid sample cell of a fluorescence spectrometer, testing the fluorescence spectrum of the compound by using a PerkinElmer LS 55 type fluorescence spectrometer, taking out a solid sample, placing the solid sample between two glass sheets, grinding the solid sample by hand, and then testing the fluorescence spectrum of the solid sample by using the fluorescence spectrometer. Fumigating with ethanol vapor for 15min, and testing the fluorescence spectrum with a fluorescence spectrometer. The grinding and solvent fumigation were repeated 4 times, and the fluorescence spectra were measured after each grinding and solvent fumigation. The results show that the fluorescence spectrum wavelength of the compound shown in the formula I generates 7nm red shift, and the fluorescence intensity is doubled. In the case of ethanol fumigation, both fluorescence intensity and wavelengthHas a recovery phenomenon. Thus, as shown in formula I
The alkali derivative shows remarkable mechanical induced fluorescence enhancement property and better fumigation recovery property.
Example 13
Structure shown in formula I
Alkali derivative mechanical force response and fumigation recovery test 3
The testing steps are as follows:
the compound of formula I was placed in the solid sample cell of a fluorescence spectrometer and the fluorescence spectrum was measured with a PerkinElmer LS 55 type fluorescence spectrometer, the solid sample was removed and placed between two glass plates, the solid compound was ground by hand and then the fluorescence spectrum was measured with a fluorescence spectrometer. And (3) fumigating with tetrahydrofuran vapor for 10min, testing the fluorescence spectrum of the sample by using a fluorescence spectrometer, and repeatedly carrying out grinding and solvent fumigation for 4 times, wherein the fluorescence spectrum is tested after grinding and solvent fumigation are carried out each time. The results show that the fluorescence spectrum wavelength of the compound shown in the formula I generates 7nm red shift, and the fluorescence intensity is doubled. In the case of tetrahydrofuran fumigation, both fluorescence intensity and wavelength have a reversion phenomenon. Thus, as shown in formula I
The alkali derivative shows remarkable mechanical induced fluorescence enhancement property and better fumigation recovery property.
Example 14
Structure of formula I
Test of the response of base derivatives to mechanical forces of various magnitudes
The testing steps are as follows:
structural general formula I
Placing the alkali derivative in a solid sample cell of a fluorescence spectrometer, testing the fluorescence spectrum of the alkali derivative by using a Perkin Elmer LS 55 type fluorescence spectrometer, taking out a solid sample, directly placing the solid under a tablet press, respectively applying pressures of 6, 12, 15, 18, 24, 27 and 30MPa, testing the fluorescence spectrum of the solid after applying the pressure by using the fluorescence spectrometer to obtain figures 8 and 9, wherein figure 8 is the structure shown in formula I
The fluorescence emission spectra of the base derivatives after different mechanical forces, FIG. 9 is that of the structure shown in formula I
The change curve of the fluorescence emission intensity of the base derivative along with the pressure after different mechanical forces act. As can be seen from FIG. 8, the structure of formula I
The fluorescence intensity of the alkali derivative is obviously changed after pressurization treatment; as can be seen from FIG. 9, when the applied pressure is 6-24 MPa, the fluorescence intensity increases significantly with the increase of the pressure and shows a substantially linear relationship. After the pressure reaches 24MPa, the change trend of the fluorescence intensity of the solid sample of the compound tends to be smooth along with the increase of the pressure.
The solid powder after fluorescence spectrum testing was directly subjected to powder X-ray diffraction testing to obtain a series of powder diffraction spectra, as shown in fig. 10. As can be seen from FIG. 10, the structure of formula I
The alkali derivative does not generate crystal form transformation under the action of mechanical force. This phenomenon is completely different from the conventional AIE molecules with mechanical induced fluorescence discoloration.
Example 15
Structure of formula I
Base derivatives after the action of mechanical forcesHeat treatment test
The testing steps are as follows:
the powder of the compound obtained in example 14, which had been subjected to a compression force of 30MPa by a tablet press, was heat-treated in an oven at 110 ℃ for 10min, 15min, 20min, 30min, 40 min and 60min, respectively, and the fluorescence spectrum was measured after the heat treatment using a PerkinElmer model LS 55 fluorescence spectrometer, the results of which are shown in FIGS. 11 and 12, and FIG. 11 shows the structure of formula I after the compression treatment
The fluorescence emission spectrum of the alkali derivative after heat treatment is shown in FIG. 12, which is the structure of formula I after pressure treatment
The fluorescence emission intensity of the base derivative as a function of the heat treatment time. As can be seen from FIGS. 11-12, the structure of formula I is shown in the process of continuously extending the heat treatment time
The fluorescence intensity of the alkali derivative only slightly fluctuates up and down and does not change obviously, which shows that the compound has good stability and better anti-interference capability when being applied to nondestructive testing of mechanical cracks.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Tetraphenylethylene modified
The alkali derivative has a structural formula shown in formula I:
2. tetraphenylethylene modified as defined in claim 1
A process for the preparation of a base derivative, characterized by comprising the steps of:
under the protection atmosphere, 4- (1,2, 2-triphenylethenyl) phenylboronic acid pinacol ester, 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f)][1,5]Diazocine, phosphate, catalyst and solvent are mixed for Suzuki coupling reaction to obtain tetraphenylethylene modified
A base derivative.
3. The preparation method according to claim 2, wherein the molar ratio of the 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine to the 4- (1,2, 2-triphenylvinyl) phenylboronic acid pinacol ester is 1 (2-3).
4. The preparation method according to claim 2, wherein the catalyst is one or more of tetratriphenylphosphine palladium, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and bis (triphenylphosphine) palladium dichloride; the dosage of the catalyst is 1-5% of the mass of 2, 8-dibromo-6H, 12H-5, 11-methylenediphenyl [ b, f ] [1,5] diazocine.
5. The method according to claim 2, wherein the phosphate is potassium phosphate and/or sodium phosphate.
6. The preparation method according to claim 2, wherein the temperature of the Suzuki coupling reaction is 80-120 ℃ and the time is 15-30 h.
7. The production method according to claim 2, wherein the solvent is an organic solvent or an organic solvent-water mixed solvent; the mass fraction of water in the organic solvent-water mixed solvent is 5-30%.
8. The preparation method according to any one of claims 2 to 7, wherein after the Suzuki coupling reaction is completed, the method further comprises a post-treatment of the obtained product liquid, and the post-treatment comprises the following steps: cooling the obtained product liquid to room temperature, and sequentially concentrating, extracting, performing column chromatography and drying to obtain tetraphenylethylene modified product
A base derivative.
9. Tetraphenylethylene modified
The method for testing the fluorescence enhancement property induced by the base derivative is characterized by comprising the following steps:
(1) the tetraphenylethylene modified of claim 1
The base derivative being treated under pressure to modify tetraphenylethylene before and after the treatment under pressure
Carrying out fluorescence intensity test on the alkali derivative; the method of the pressure treatment includes grinding or pressurizing using a tablet press;
(2) for tetraphenylethylene modified after pressure treatment in (1)
Solvent fumigation of base derivatives, modification of tetraphenylethylene by solvent fumigation
The fluorescence intensity of the base derivative is tested;
(3) for tetraphenylethylene modified after pressure treatment in (1)
Subjecting the base derivative to a powder X-ray diffraction test;
(4) for tetraphenylethylene modified after pressure treatment in (1)
By heat treatment of alkali derivatives, modified by tetraphenylethylene after heat treatment
Carrying out fluorescence intensity test on the alkali derivative;
the steps (2), (3) and (4) have no requirement on time sequence.
10. The test method according to claim 9, wherein the grinding is tetraphenylethylene modified
The alkali derivative is placed between two glass sheets and then manually ground; the pressure for pressurizing by using the tablet press is 3-30 MPa;
the solvent used for solvent fumigation is one or more of dichloromethane, trichloromethane, ethanol, methanol and tetrahydrofuran;
the temperature of the heat treatment is 100-120 ℃, and the time is 10-60 min.
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| CN104926819A (en) * | 2015-05-15 | 2015-09-23 | 江苏师范大学 | Synthesis method of 2,8-diaryl(amino) Troger's base derivatives |
| CN110305114A (en) * | 2018-03-27 | 2019-10-08 | 武汉尚赛光电科技有限公司 | A kind of anthryl fluorescent material and its application causing fluorescence discoloration property with aggregation inducing fluorescence and pressure |
| CN110615802A (en) * | 2019-10-24 | 2019-12-27 | 江苏师范大学 | Benzimidazole quinazoline derivative and preparation method and application thereof |
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| CN104926819A (en) * | 2015-05-15 | 2015-09-23 | 江苏师范大学 | Synthesis method of 2,8-diaryl(amino) Troger's base derivatives |
| CN110305114A (en) * | 2018-03-27 | 2019-10-08 | 武汉尚赛光电科技有限公司 | A kind of anthryl fluorescent material and its application causing fluorescence discoloration property with aggregation inducing fluorescence and pressure |
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