CN108003859A - Piezochromic fluorescent molecule and preparation method and application thereof - Google Patents
Piezochromic fluorescent molecule and preparation method and application thereof Download PDFInfo
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- CN108003859A CN108003859A CN201711373934.XA CN201711373934A CN108003859A CN 108003859 A CN108003859 A CN 108003859A CN 201711373934 A CN201711373934 A CN 201711373934A CN 108003859 A CN108003859 A CN 108003859A
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- piezallochromy
- acid
- fluorescence molecule
- compound
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000004982 aromatic amines Chemical class 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XHTYQFMRBQUCPX-UHFFFAOYSA-N 1,1,3,3-tetramethoxypropane Chemical compound COC(OC)CC(OC)OC XHTYQFMRBQUCPX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 7
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- -1 trifluoroacetic acid radical ion Chemical class 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims 1
- 235000013849 propane Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 64
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 52
- 239000007787 solid Substances 0.000 abstract description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 22
- 230000002776 aggregation Effects 0.000 abstract description 16
- 238000004220 aggregation Methods 0.000 abstract description 16
- 238000000295 emission spectrum Methods 0.000 abstract description 15
- 230000008859 change Effects 0.000 abstract description 9
- 238000009825 accumulation Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 238000003958 fumigation Methods 0.000 abstract 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 238000000227 grinding Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 0 *c(cc1)ccc1[N-]C=C Chemical compound *c(cc1)ccc1[N-]C=C 0.000 description 2
- 235000004237 Crocus Nutrition 0.000 description 2
- 241000596148 Crocus Species 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002929 anti-fatigue Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003471 mutagenic agent Substances 0.000 description 2
- 231100000707 mutagenic chemical Toxicity 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- MJODAASSYQGUAX-UHFFFAOYSA-N CC[O](C)c(cc1)ccc1N Chemical compound CC[O](C)c(cc1)ccc1N MJODAASSYQGUAX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical class [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/30—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups quaternised
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04L—TRANSMISSION OF DIGITAL INFORMATION, e.g. TELEGRAPHIC COMMUNICATION
- H04L9/00—Cryptographic mechanisms or cryptographic arrangements for secret or secure communications; Network security protocols
- H04L9/08—Key distribution or management, e.g. generation, sharing or updating, of cryptographic keys or passwords
- H04L9/0861—Generation of secret information including derivation or calculation of cryptographic keys or passwords
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Computer Security & Cryptography (AREA)
- Computer Networks & Wireless Communication (AREA)
- Signal Processing (AREA)
Abstract
The invention provides a piezochromic fluorescent molecule and a preparation method and application thereof. The piezochromic fluorescent molecule provided by the invention has aggregation-induced emission property, and under the action of pressure, the original crystalline state of the compound is changed into an amorphous state, so that the accumulation mode under the solid state condition is changed, and the change of an emission spectrum is further caused; the compound is transformed from amorphous state to crystalline state after fumigation, and has piezochromic property. Experimental results show that the piezochromic fluorescent molecule provided by the invention has good solubility in dimethyl sulfoxide, but hardly dissolves in dichloromethane, can form a nano aggregate, and has aggregation-induced luminescence characteristics. In addition, the solid luminescent color is from yellow green light to orange yellow light, the change of the solid luminescent color can be obviously observed under a 365nm ultraviolet lamp after the action of pressure, and the original luminescent color can be recovered under the fumigation of methanol steam.
Description
Technical field
The present invention relates to photoelectric functional material technology field, more particularly to a kind of piezallochromy fluorescence molecule and its preparation side
Method and application.
Background technology
In recent years, fluorescence molecule is extensive due to having in fields such as oled light electrical part, biology sensor, information securities
Application value, has caused the strong interest of vast research works.However, conventional fluorescent compound presents in the solution
High luminous efficiency, fluorescence intensity is shown as in coherent condition and weakens or even is quenched, here it is common aggregation inducing fluorescence
Quenching effect (aggregation caused quenching, ACQ).In view of fluorescent material is usually with aggregation or solid film shape
Formula uses, and ACQ phenomenons seriously limit the application prospect of fluorescent material under specific circumstances.
2001, this loyalty academician seminar of Tang reported a kind of molecule with propeller arrangement, they have shows with ACQ
As opposite luminescent behavior：Fluorescence is very weak in the solution or does not shine for the quasi-molecule, but in solid-state or coherent condition, then produces
Raw strong fluorescence.They this phenomenon be named as aggregation-induced emission (aggregation-induced emission,
AIE) phenomenon.AIE phenomenons and traditional ACQ phenomenons are just the opposite, and organic fluorescence can be further widened using this new features
Application of the compound in solid or coherent condition field.Further, since point of most of molecules with AIE properties with distortion
Sub- conformation, causes its packing of molecules relative loose, and after being subject to power to stimulate, intramolecular action power changes, and causes molecule
Accumulation mode changes so that material becomes another orderly or partial order, disordered structure, material from a kind of ordered structure
The photophysical property of material changes therewith, i.e. piezallochromy property.Then after heating, solvent such as fumigate at the processing, the heap of molecule
Product mode can revert to it is original, realize fluorescence color change invertibity.Fluorescent material with piezallochromy property is one
The new intellectual material of kind, it has very extensive in fields such as strain gauge, information storage, fluorescent switch and luminescent devices
Application.
2014 Nian Liurui seminars, which report, using fluorine boron complexes as core, introduces bowl-shape phenthazine molecule as power supply
Sub- substituent, the compound present AIE characteristics.In addition under pressure, shining for compound is changed into red from yellow,
Under dichloromethane steam, glow color can return to initial yellow (Chem.Commun., 2014,50,12951-
12954).You seminars in 2016 are reported with [1,2,4] triazolone-[1,5-a] pyrimidine as parent, are introduced respectively different
Substituent, it is adjustable to realize glow color, at the same obtain a series of piezochromic materials (J.Am.Chem.Soc.2016,
138,12803-12812).But up to the present it has been reported that the luminescent material with piezallochromy property it is also seldom.
The content of the invention
It is an object of the invention to provide a kind of piezallochromy fluorescence molecule and its preparation method and application.The present invention provides
Piezallochromy fluorescence molecule there is aggregation-induced emission characteristic and piezallochromy characteristic.
The present invention provides a kind of piezallochromy fluorescence molecule, has the chemical constitution shown in Formulas I：
A in the Formulas I-For acid ion；
R is group shown in R1 or R3 in the Formulas I：
Preferably, the acid ion includes chlorion, sulfate ion, acetate ion or trifluoroacetic acid radical ion.
The present invention provides a kind of preparation method of piezallochromy fluorescence molecule described in above-mentioned technical proposal, including following step
Suddenly：
(1) 1,1,3,3- tetramethoxy propane, arylamine and organic solvent are mixed, obtains mixed solution；The aryl
Amine is aniline or para-bromoaniline；
(2) mixed solution that the step (1) obtains is cooled to -5~5 DEG C, acid solution is added dropwise, be hydrolyzed and nucleophilic
Addition reaction, obtains piezallochromy fluorescence molecule.
Preferably, organic solvent includes one kind or more in methanol, ethanol, acetonitrile and tetrahydrofuran in the step (1)
Kind.
Preferably, the acid in the step (2) in acid solution and the molar ratio of 1,1,3,3- tetramethoxy propane for (1~
4):1。
Preferably, the speed being added dropwise in the step (2) is 0.25~0.4mL/min.
Preferably, the mass concentration of the acid solution is 30~40%.
Preferably, the acid solution includes a kind of aqueous solution in hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid.
The present invention provides the application of piezallochromy fluorescence molecule described in above-mentioned technical proposal, the pressure described in claim 1
Mutagens color fluorescence molecule forms confidential information to be added.
Preferably, the encryption for being encrypted as realizing information by carrying out the piezallochromy fluorescence molecule pressurization；Institute
It is that the decryption of information is realized by being fumigated to piezallochromy fluorescence molecule progress steam to state decryption.
The present invention provides a kind of piezallochromy fluorescence molecule, has the chemical constitution shown in Formulas I：
A in the Formulas I-For acid ion；
R is group shown in R1 or R3 in the Formulas I：
Piezallochromy fluorescence molecule provided by the invention has aggregation-induced emission property, and the principle of piezallochromy comes from point
Transformation between sub- crystalline state and amorphous state.The present invention result in chemical combination by the arylamine in molecular end introducing different structure
Thing is crystalline state in solid-state with different accumulation modes, compound in solid-state, and under pressure, compound is by original
Crystalline state is changed into amorphous state, changes the accumulation mode in the case of its solid-state, and then causes the change of emission spectrum；Smoked
Compound is changed into crystalline state from amorphous state again after steaming, has piezallochromy performance.Test result indicates that pressure provided by the invention
Mutagens color fluorescence molecule has good dissolubility in dimethyl sulfoxide (DMSO), and does not almost dissolve in methylene chloride, can be formed
Micelle-like Nano-structure of Two, has aggregation-induced emission characteristic.In addition solid luminescence color is from green-yellow light to orange light, in the effect of pressure
Afterwards, can be clearly under 365nm ultraviolet lamps observe solid luminescence color change, while can be with the case where methanol steam is fumigated
Recover original glow color.
Also, piezallochromy fluorescence molecule provided by the invention repeatedly grinds and fumigates, its aggregation-induced emission
It can illustrate that the anti-fatigue performance of compound is more excellent with the not obvious decay of piezallochromy performance.
In addition, the preparation method synthesis step of piezallochromy fluorescence molecule provided by the invention is short, yield it is higher (55~
83%), raw material is cheap, and holistic cost is low.
Brief description of the drawings
Fig. 1 be in the embodiment of the present invention 1~2 and comparative example 1~3 compound in dimethyl sulphoxide solution it is ultraviolet-
Visible absorption spectra；
Fig. 2 is the preferred configuration of compound ground state in the embodiment of the present invention 1~2 and comparative example 1~3, and highest occupies rail
The Cloud Distribution in road and lowest unoccupied molecular orbital；
Fig. 3 be in the embodiment of the present invention 1~2 and comparative example 1~3 compound in the transmitting light of dimethyl sulphoxide solution
Spectrum；
Fig. 4 is the emission spectrum of compound solid state in the embodiment of the present invention 1~2 and comparative example 1~3；
Fig. 5 is piezallochromy fluorescence molecule in the embodiment of the present invention 1 in dimethyl sulfoxide (DMSO)-dichloromethane mixed system
Emission spectrum and the relative intensity figure of transmitting；
Fig. 6 is piezallochromy fluorescence molecule in comparative example 1 of the present invention in dimethyl sulfoxide (DMSO)-dichloromethane mixed system
Emission spectrum and the relative intensity figure of transmitting；
Fig. 7 is piezallochromy fluorescence molecule in the embodiment of the present invention 2 in dimethyl sulfoxide (DMSO)-dichloromethane mixed system
Emission spectrum and the relative intensity figure of transmitting；
Fig. 8 is piezallochromy fluorescence molecule in comparative example 2 of the present invention in dimethyl sulfoxide (DMSO)-dichloromethane mixed system
Emission spectrum and the relative intensity figure of transmitting；
Fig. 9 be comparative example 3 of the present invention in emission spectrum of the compound in dimethyl sulfoxide (DMSO)-dichloromethane mixed system with
The relative intensity figure of transmitting；
Figure 10 is that the grinding of piezallochromy fluorescence molecule and methanol fumigate front and rear fluorescence spectrum in the embodiment of the present invention 1 and 2；
Figure 11 is the wavelength change that piezallochromy fluorescence molecule circular grinding and methanol are fumigated in the embodiment of the present invention 1 and 2；
Figure 12 be in the embodiment of the present invention 1 and 2 piezallochromy fluorescence molecule original, grinding and it is stifling in the case of X penetrate
Ray diffraction diagram；
Figure 13 is the information encrypt-decrypt schematic diagram of piezallochromy fluorescence molecule in the embodiment of the present invention 1.
Embodiment
The present invention provides a kind of piezallochromy fluorescence molecule, has the chemical constitution shown in Formulas I：
A in the Formulas I-For acid ion；
R is one kind in group shown in R1 or R3 in the Formulas I：
Piezallochromy fluorescence molecule provided by the invention has aggregation-induced emission property, and under pressure, changes
Compound is changed into amorphous state by original crystalline state, changes the accumulation mode in the case of its solid-state, and then causes transmitting light
The change of spectrum；Compound is changed into crystalline state from amorphous state again after stifling, has piezallochromy performance.
The present invention provides a kind of preparation method of piezallochromy fluorescence molecule described in above-mentioned technical proposal, including following step
Suddenly：
(1) 1,1,3,3- tetramethoxy propane, arylamine and organic solvent are mixed, obtains mixed solution；The aryl
Amine is aniline or para-bromoaniline；
(2) mixed solution that the step (1) obtains is cooled to -5~5 DEG C, acid solution is added dropwise, be hydrolyzed and nucleophilic
Addition reaction, obtains piezallochromy fluorescence molecule.
The present invention mixes 1,1,3,3- tetramethoxy propane, arylamine and organic solvent, obtains mixed solution.In this hair
In bright, the arylamine is aniline or para-bromoaniline.In the present invention, when the arylamine is aniline and para-bromoaniline, obtain
Product difference corresponding I in R be R1 and R3 compound.The present invention is to the 1,1,3,3- tetramethoxy propanes and arylamine
Ratio there is no special restriction, be adjusted according to chemical equation.
In the present invention, the organic solvent is preferably polar organic solvent, more preferably including methanol, ethanol, acetonitrile and
One or more in tetrahydrofuran, more preferably ethanol.The present invention does not have special restriction to the dosage of the organic solvent,
Can dissolve reaction raw materials.In the present invention, the organic solvent and 1, the mass ratio of 1,3,3- tetramethoxy propane
Preferably (10~20):1, more preferably (14~16):1.
Operation of the present invention to the mixing of the 1,1,3,3- tetramethoxy propanes, arylamine and organic solvent is no special
Limit, using the technical solution well known to those skilled in the art for preparing mixed solution.
After obtaining mixed solution, the mixed solution is cooled to -5~5 DEG C by the present invention, and acid solution is added dropwise, is hydrolyzed
And nucleophilic addition, obtain piezallochromy fluorescence molecule.In the present invention, the mixed solution is preferably cooled to -3~3 DEG C,
More preferably 0 DEG C.In the present invention, the cooling provides suitable temperature conditionss for sequential hydrolysis and nucleophilic addition.
In the present invention, the acid in the acid solution and the molar ratio of 1,1,3,3- tetramethoxy propane be preferably (1~
4):1, more preferably (2~3):1.In the present invention, the mass concentration of the acid solution is preferably 30~40%, more preferably
32~38%, it is most preferably 34~36%.In the present invention, the acid solution preferably includes hydrochloric acid, sulfuric acid, acetic acid and trifluoro second
A kind of aqueous solution in acid.In the present invention, A in the hydrochloric acid, sulfuric acid, acetic acid and trifluoroacetic acid difference corresponding I-For chlorine
Ion, sulfate ion, the compound of acetate ion and trifluoroacetic acid radical ion.In the present invention, the acid solution plus
Enter and provide acid reaction environment with nucleophilic addition to hydrolyze, and be capable of providing acid ion, form stable salt.
In the present invention, the speed of the dropwise addition of the acid solution is preferably 0.25~0.4mL/min, more preferably 0.27~
0.35mL/min, is most preferably 0.3mL/min.In the present invention, the dropwise addition can control the speed of hydrolysis, reduce accessory substance
Production.
In the present invention, the hydrolysis and nucleophilic addition carry out step by step successively, and 1,1,3,3- tetramethoxy propane exists
Acid solution be added dropwise during hydrolysis obtain malonaldehyde, then with arylamine nucleophilic addition.
After the completion of hydrolysis and nucleophilic addition, product of the present invention preferably by the hydrolysis and nucleophilic addition carries out
Separation of solid and liquid, obtains piezallochromy fluorescence molecule.Operation no special restriction of the present invention to the separation of solid and liquid, using this
The operation of separation of solid and liquid known to field technology personnel.In the present invention, the separation of solid and liquid preferably includes filtering successively
And drying.The present invention does not have special restriction to the filtering and dry technical solution, using known to those skilled in the art
Filtering and drying technical solution.
Present invention also offers the application of piezallochromy fluorescence molecule described in above-mentioned technical proposal, with above-mentioned technical proposal institute
State piezallochromy fluorescence molecule and form confidential information to be added.The present invention is preferably by pressurizeing the piezallochromy fluorescence molecule
Realize the encryption of information, the decryption of information is realized by being fumigated to piezallochromy fluorescence molecule progress steam.
In the present invention, the application of the piezallochromy fluorescence molecule preferably includes：With containing piezallochromy fluorescence molecule
Solution confidential information to be added is stamped on the paper of yellow, obtain the paper with encryption information；By described with encryption information
Paper is fumigated in the steam of easy volatile solvent.
Confidential information to be added is preferably stamped on the paper of yellow by the present invention with the solution containing piezallochromy fluorescence molecule, is obtained
To the paper with encryption information.In the present invention, the solvent in the solution containing piezallochromy fluorescence molecule is preferably two
Methyl sulfoxide.The present invention does not have special restriction to the concentration of the solution of the piezallochromy fluorescence molecule and the pressure of coining,
It can ensure that information completely develops the color.
In the present invention, the paper of the yellow with it is pressurized after piezallochromy fluorescence molecule luminous face in the UV lamp
Color is identical, can hide the encryption information of piezallochromy fluorescence molecule formation.
When needing decryption, the present invention preferably fumigates the paper with encryption information in the steam of easy volatile solvent.
In the present invention, the easy volatile solvent is preferably the one or more in methanol, ethanol, acetone, tetrahydrofuran and acetonitrile.
In the present invention, the stifling pressure is preferably the vapour pressure of easy volatile solvent at normal temperatures.In the present invention, it is described stifling
Time is preferably 5~20min, more preferably 10~15min.In the present invention, the piezallochromy fluorescence molecule is after stifling
Recover its original color in the UV lamp, different from the yellow of paper, show encryption information.
In order to further illustrate the present invention, with reference to embodiment to piezallochromy fluorescence molecule provided by the invention and its
Preparation method and application are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1:
The synthesis of N- ((1E) -3- (phenyl imido) propyl- 1- alkene -1- bases) anilinechloride (N1), reaction equation are as follows：
1,1,3,3- tetramethoxy propane 3.284g (0.02mol, 1eq.), aniline are added in bis- mouthfuls of flasks of 100mL
3.720g (0.04mol, 2eq.) and 50ml absolute ethyl alcohols, stirring are completely dissolved rear solution and are cooled to 0 DEG C, use constant pressure funnel
4ml concentrated hydrochloric acids were slowly added dropwise in 15 minutes, is added dropwise and continues that 1~2h is stirred at room temperature, there is yellow solid precipitation, filter,
Vacuum drying obtains crocus product, yield 55% after water and ethanol wash filter cake 3 times respectively.
Testing result：1H NMR δ 12.70 (s, 2H), 8.925 (d, J=6.0Hz, 2H), 7.43-7.50 (m, 8H), 7.25
(t, J=4.0Hz, 2H), 6.51 (t, J=12Hz, 1H),
Elemental analysis：Packet type C15H15ClN2。
Calculated value：C,69.63；H,5.84；N,10.83.
Actual measured value：C,69.60；H,5.87；N,10.82.
High resolution mass spectrum：Quasi-molecular ions calculated value [M-Cl-]:223.1229。
Measured value:223.1230.
Comparative example 1:
The synthesis of 4- methyl-N- ((1E) -3- (to toluene imido grpup) propyl- 1- alkene -1- bases) anilinechloride (N2), reaction
Equation is as follows：
Process is same as embodiment 1, and reactant aniline simply is changed to para-totuidine, and vacuum drying obtains yellow product, receives
Rate is 79%.
Testing result：1H NMR δ 12.55 (d, J=8.0Hz, 2H), 8.79 (q, J=12Hz, J=4.0Hz, 2H), 7.29
(q, J=8Hz, J=4.0Hz, 8H), 6.43 (t, J=8.0Hz, 1H), 2.31 (s, 6H),
Elemental analysis：Molecular formula C17H19ClN2。
Calculated value：C,71.19；H,6.68；N,9.77.
Actual measured value:C,71.13；H,6.64；N,9.71.
High resolution mass spectrum：Quasi-molecular ions calculated value [M-Cl-]:251.1543。
Measured value:251.1545.
Embodiment 2:
The synthesis of the bromo- N- of 4- ((1E) -3- ((4- bromobenzenes) imido grpup) propyl- 1- alkene -1- bases) anilinechloride (N3), reaction
Equation is as follows：
Process is same as embodiment 1, and reactant aniline simply is changed to para-bromoaniline, and vacuum drying obtains yellow product, receives
Rate is 83%.
Testing result：1H NMR δ 12.74 (s, 2H), 8.815 (d, J=6.0Hz, 2H), 7.70 (d, J=4.0Hz, 4H),
7.37 (d, J=4.0Hz, 4H), 6.51 (t, J=12Hz, 1H).
Elemental analysis：Molecular formula C15H13Br2ClN2。
Calculated value：C,43.25；H,3.15；N,6.73.
Actual measured value:C,43.29；H,3.13；N,6.70.
High resolution mass spectrum：Quasi-molecular ions calculated value [M-Cl-]:380.9440。
Measured value:380.9436.
Comparative example 2：
The synthesis of 4- nitros-N- ((1E) -3- ((4- nitrobenzenes) imido grpup) propyl- 1- alkene -1- bases) anilinechloride (N4),
Reaction equation is as follows：
Process is same as embodiment 1, and reactant aniline simply is changed to paranitroanilinum, and vacuum drying obtains yellow product,
Yield is 65%.
Testing result：1H NMR δ 13.43 (s, 2H), 9.075 (d, J=6.0Hz, 2H), 8.385 (d, J=6.0Hz,
4H), 7.645 (d, J=6.0Hz, 4H), 6.72 (t, J=12Hz, 1H).
Elemental analysis：Molecular formula C15H13ClN4O4。
Calculated value：C,51.66；H,3.76；N,16.07.
Actual measured value:C,51.69；H,3.78；N,16.02.
High resolution mass spectrum：Quasi-molecular ions calculated value [M-Cl-]:313.0937。
Measured value:313.0932.
Comparative example 3：
The synthesis of N- ((1E) -3- (naphthalene -1- imido grpups) propyl- 1- alkene -1- bases) naphthalene -1- amine hydrochlorates (N5), reactional equation
Formula is as follows：
Process is same as embodiment 1, and reactant aniline simply is changed to naphthalidine, and vacuum drying obtains crocus product, receives
Rate is 78%.
Testing result：1H NMR δ 12.90 (s, 2H), 8.83 (t, J=12.0Hz, 2H), 8.43 (d, J=4.0Hz, 2H),
8.03 (t, J=4.0Hz, 2H), 7.94 (d, J=4.0Hz, 2H), 7.62-7.71 (m, 8H), 7.15 (t, J=12Hz, 1H).
Elemental analysis：Molecular formula C23H19ClN2。
Calculated value：C,76.98；H,5.34；N,7.81.
Actual measured value:C,76.91；H,5.39；N,7.82.
High resolution mass spectrum：Quasi-molecular ions calculated value [M-Cl-]:323.1543。
Measured value:323.1549.
Embodiment 3
The uv-visible absorption spectra test of 1~N5 of compound N
Using dimethyl sulfoxide (DMSO) as solvent, 1~N5 of compound N is made into concentration as 1 × 10 respectively-5The solution of mol/L.In room
Under the conditions of temperature, using TU-1900UV type ultraviolet-visible photometers, with the quartz colorimetric utensil of 1cm, 200~600nm wave bands into
Row ultra-violet absorption spectrum scans, uv-visible absorption spectras of the measurement 1~N5 of compound N in dimethyl sulphoxide solution, test
The result is shown in Figure 1.The dimethyl sulphoxide solution of these compounds all shows stronger absorption in ultraviolet-visible light area, with reference to compared with
Strong molar absorption coefficient, the absworption peak of no fine structure and certain solvation effect, can be attributed to 1 π, π * transition
Mix certain Intramolecular electron transfer (ICT).
Embodiment 4
Compound N 1~N5 quantum chemical methods
In order to understand compound N 1~N5 ground state electron properties in depth, optimize to obtain energy most using 09 Gauss program
After low space conformation, the calculating of density functional theory (DFT) is carried out to 1~N5 of compound N with B3LYP/6-31g (d) units.
Fig. 2 illustrates that the compound in addition to N5, the right side of other compounds is almost coplanar, and the aromatic rings on the left side and principal plane
There are certain distortion.Two naphthalene nucleus and center section in 5 molecule of compound N are using the space conformation of distortion.In addition,
Observe that dihedral angle is influenced be subject to distinct fragrance ring in the optimized geometries of these molecules.With NO2Substituted compound
The dihedral angle of N4 is 40.5 °, all bigger than the dihedral angle of other compounds.Additionally due to approximate coplanar steric configuration, chemical combination
Almost delocalization is in whole molecule for the highest occupied molecular orbital of thing N1-N4 and π-electronics of lowest unoccupied molecular orbital, and corresponding to be, N5 is most
High occupied orbital and lowest unoccupied molecular orbital distribution is mainly distributed on two naphthalene nucleus, therefore is observed that some electric charge transfers are special
Property.
Embodiment 5
The emission spectrum test of 1~N5 of compound N
Using dimethyl sulfoxide (DMSO) as solvent, 1~N5 of compound N is made into concentration as 1 × 10-5The solution of mol/L.In room temperature bar
Under part, transmitting light of the 1~N5 of Hitachi F-4600 fluorescence spectrophotometer measurement compound Ns in dimethyl sulphoxide solution is used
Spectrum, test result are shown in Fig. 3.The transmitting of all compounds is respectively positioned on blue green light region.Wherein 1~N4 of compound N is in the solution
Variation in emission wavelength is little, illustrate phenyl ring up conversion it is different supply electron withdrawing group, be not significantly affected by compound molten
Emission level in liquid.The launch wavelength of compound N 5 has obvious red shift with respect to other several compounds, this is probably due to big
Conjugated system existing for reason.
Embodiment 6
The solid-state emission spectrum test of 1~N5 of compound N
At ambient temperature, 1~N5 of compound N solid powders are added in solid sample groove, is excited and surveyed with 360nm wavelength
The solid emissive spectrum of compound is tried, test result is shown in Fig. 4.The transmitting of all compounds is located at yellow green to orange-yellow region.
Compared with liquid is launched, emission spectrum and the substituent of compound have very big relation.The emission peak difference of 1~N5 of compound N
Positioned at 561nm, 549nm, 593nm, 531nm and 622nm, 580nm.
Embodiment 7
The aggregation inducing emission spectrum test of 1~N5 of compound N
1~N5 of compound N has good dissolubility in dimethyl sulfoxide (DMSO), while is not almost dissolved in dichloromethane,
Therefore we select the aggregation inducing emission characteristic of dimethyl sulfoxide (DMSO)-dichloromethane system test compound.Respectively by compound
Different volumes are dissolved or dispersed in than in dimethyl sulfoxide (DMSO)-dichloromethane liquid of mixing, using Hitachi's F-4600 fluorescence spectrophotometers
The emissive porwer of photometer test mixing system, the result is shown in Fig. 5-9.As seen from the figure, such compound is respectively provided with certain aggregation
Induced luminescence property.
Embodiment 8
Compound N 1 and N3 grindings and stifling front and rear fluorescence spectrum
Compound N 1 and N3 fumigate front and rear emission spectrum and see Figure 10 in pressure effect and solvent, and compound N 1 and N3 are placed in
In agate mortar, solid is firmly ground, until them, the glow color under 365nm ultraviolet lamps is changed into yellow green and yellow respectively,
Solid sample after grinding is collected and is added in solid sample groove, solid emissive spectrum after test grinding, it can be found that grinding
Solid emissive peak position afterwards is converted near 518nm and 552nm by original 561nm and 593nm respectively.Then after grinding
Solid sample be put into the steam atmosphere of methanol, observe after its color returns to initial conditions and test its solid emissive spectrum,
The results show solid emissive peak position nearby returns to 561nm and 593nm again by 518nm and 552nm.Two compounds are in pressure
Under the action of steam, it is possible to achieve the movement of launch wavelength about 40nm.In addition as shown in figure 11, grinding and stifling experiment can
With repeatedly not obvious decay, illustrate that the anti-fatigue performance of compound is more excellent.
Embodiment 9
Compound N 1 and N3 grindings and it is stifling under powder x-ray diffraction
Compound N 1 and N3 is original, and sample stifling again carries out powder x-ray diffraction, original chemical combination after grinding and grinding
Thing N1 and N3 show it is many point and thin diffraction maximum, the solid for illustrating them are crystalline state, after being fully ground almost without
Obvious diffraction maximum, it is amorphous state to illustrate their solid.Under pressure, compound is changed into nothing by original crystalline state
Shape state, changes the accumulation mode in the case of its solid-state, and then cause the change of emission spectrum.In addition the chemical combination after stifling
Thing presents many diffraction maximums again, illustrates in the case where solvent is fumigated, and compound is changed into crystalline state from amorphous state again.This explanation N1 and
The piezallochromy reason of N3 compounds derives from crystal-unbodied transformation.
Embodiment 10
Using the piezallochromy of compound N 1 and the property of gas-discoloration, a kind of promising data storage material is developed
Material, encrypts and decrypts for information.Encryption and decryption schematic diagram are as shown in figure 13.Select dyestuff (E) -4- (4- (diethyl) benzene
Methylene) benzoic acid offer background colour.Filter paper is soaked 10 minutes in the dichloromethane solution of dyestuff, after being dried at room temperature for
The paper of a yellow is obtained, which sends green-yellow light under ultraviolet light.In encrypting stage, with containing alphabetical " NJTECH " seal
Special " ink " methanol solution has been dipped in (containing compound N 1, concentration 10-4Mol/L), it is alphabetical on lid on the filter paper of yellow
" NJTECH ", after dry, under natural light and 365nm ultraviolet lamps, due to color is similar, be invisible to the naked eye any word
Mother, this shows that data encryption is completed.In decryption phase, filter paper is exposed to a period of time in methanol steam, in 365nm ultraviolet lights
According to lower it will be clear that the yellow emission of character " NJTECH ".These the result shows that compound N 1 in data security protecting side
Face has potential application value.
As can be seen from the above Examples and Comparative Examples, piezallochromy fluorescence molecule provided by the invention has aggregation inducing
Luminosity, and under pressure, compound is changed into amorphous state by original crystalline state, in the case of changing its solid-state
Accumulation mode, and then cause the change of emission spectrum；Compound is changed into crystalline state from amorphous state again after stifling, has
Piezallochromy performance.
The above is only the preferred embodiment of the present invention, not makees limitation in any form to the present invention.Should
Point out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of piezallochromy fluorescence molecule, has the chemical constitution shown in Formulas I：
A in the Formulas I-For acid ion；
R is group shown in R1 or R3 in the Formulas I：
2. piezallochromy fluorescence molecule according to claim 1, it is characterised in that the acid ion include chlorion,
Sulfate ion, acetate ion or trifluoroacetic acid radical ion.
3. the preparation method of piezallochromy fluorescence molecule, comprises the following steps described in claim 1：
(1) 1,1,3,3- tetramethoxy propane, arylamine and organic solvent are mixed, obtains mixed solution；The arylamine is
Aniline or para-bromoaniline；
(2) mixed solution that the step (1) obtains is cooled to -5~5 DEG C, acid solution is added dropwise, be hydrolyzed and nucleophilic addition
Reaction, obtains piezallochromy fluorescence molecule.
4. preparation method according to claim 3, it is characterised in that organic solvent includes methanol, second in the step (1)
One or more in alcohol, acetonitrile and tetrahydrofuran.
5. preparation method according to claim 3, it is characterised in that the acid and 1,1 in the step (2) in acid solution,
The molar ratio of 3,3- tetramethoxy propanes is (1~4):1.
6. preparation method according to claim 3, it is characterised in that the speed being added dropwise in the step (2) for 0.25~
0.4mL/min。
7. the preparation method according to claim 3 or 6, it is characterised in that the mass concentration of the acid solution for 30~
40%.
8. preparation method according to claim 7, it is characterised in that the acid solution includes hydrochloric acid, sulfuric acid, acetic acid and three
A kind of aqueous solution in fluoroacetic acid.
9. application of the piezallochromy fluorescence molecule in information encrypt-decrypt described in claim 1, it is characterised in that use right
It is required that the 1 piezallochromy fluorescence molecule forms confidential information to be added.
10. application according to claim 9, it is characterised in that described to be encrypted as by the piezallochromy fluorescence point
Son carries out the encryption that information is realized in pressurization；The decryption is to fumigate realization by carrying out steam to the piezallochromy fluorescence molecule
The decryption of information.
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| CN112851582A (en) * | 2021-01-07 | 2021-05-28 | 温州大学 | Piezochromic material, encryptable material prepared from piezochromic material and decryption method |
| CN114478357A (en) * | 2022-04-15 | 2022-05-13 | 江苏新视界先进功能纤维创新中心有限公司 | Halogen bond-containing piezochromic aggregation-induced emission molecule |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180506A (en) * | 2018-10-17 | 2019-01-11 | 湖州师范学院 | A kind of two kinds of static pressure cause ratio tenebrescent molecules and preparation method thereof shown |
| CN109180506B (en) * | 2018-10-17 | 2021-07-16 | 湖州师范学院 | Two-display static pressure ratio color-changing fluorescent molecule and preparation method thereof |
| CN112482263A (en) * | 2020-11-12 | 2021-03-12 | 招商局重庆交通科研设计院有限公司 | Overload detection road surface and vehicle overload detection method |
| CN112851582A (en) * | 2021-01-07 | 2021-05-28 | 温州大学 | Piezochromic material, encryptable material prepared from piezochromic material and decryption method |
| CN112851582B (en) * | 2021-01-07 | 2022-02-25 | 温州大学 | Piezochromic material, encryptable material prepared from piezochromic material and decryption method |
| CN114478357A (en) * | 2022-04-15 | 2022-05-13 | 江苏新视界先进功能纤维创新中心有限公司 | Halogen bond-containing piezochromic aggregation-induced emission molecule |
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