CN115108940B - Hydrazone-based bistable chiral optical switch material and preparation and application thereof - Google Patents
Hydrazone-based bistable chiral optical switch material and preparation and application thereof Download PDFInfo
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- 150000007857 hydrazones Chemical class 0.000 title claims abstract description 54
- 230000003287 optical effect Effects 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 15
- 239000007787 solid Substances 0.000 claims abstract description 25
- 238000007699 photoisomerization reaction Methods 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 14
- 230000002441 reversible effect Effects 0.000 claims abstract description 13
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004020 luminiscence type Methods 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 230000000638 stimulation Effects 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 abstract description 6
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 238000010586 diagram Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- XYZWMVYYUIMRIZ-UHFFFAOYSA-N 4-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(Br)C=C1 XYZWMVYYUIMRIZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001748 luminescence spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IGJDINDKLXPNKE-UHFFFAOYSA-N 1-N,3-N-dimethyl-2H-pyridine-1,3-diamine Chemical compound CNN1CC(=CC=C1)NC IGJDINDKLXPNKE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- 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
- C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
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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
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/0126—Opto-optical modulation, i.e. control of one light beam by another light beam, not otherwise provided for in this subclass
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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Abstract
The invention discloses a hydrazone-based bistable chiral optical switch material which is characterized in that a hydrazone molecular switch is taken as a framework, N-dimethylaniline is introduced at one end of the hydrazone molecular switch as an electron donor, a benzene ring is modified at the other end of the hydrazone molecular switch as an electron acceptor, and a chiral center is introduced at an ester side chain. In a solution state, the optical switch material with the push-pull electronic structure can realize the transformation of the photophysical property under the irradiation of visible light/ultraviolet light, and has good photoinduced reversible isomerization characteristic; the chiral optical switch material has the advantages of long thermal half-life period, high photoisomerization quantum yield, high stability, switchable solution/solid luminescence and the like; the chiral optical switch material has the property of photoinduced reversible isomerism in a solid state, circular polarization luminescence signals of the chiral optical switch material can be effectively regulated and controlled after optical stimulation, and the chiral optical switch material has repeatability, and can provide a new effective path for multiple anti-counterfeiting and information encryption applications.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a hydrazone-based bistable chiral optical switch material, and preparation and application thereof.
Background
The chiral switch material has wide potential application prospect in the fields of information storage, optical sensing, chiral biological imaging, anti-counterfeiting encryption and the like, and draws attention of the person skilled in the art. In recent years, a plurality of stimulus-responsive chiral switching materials are developed successively, and the chiral switching materials are favored because light itself has the characteristics of cleanness, no pollution, precise adjustment and control of intensity and wavelength, and the like.
At present, a main preparation strategy of a chiral optical switch material is to modify a chiral center on a molecular optical switch to be used as a photosensitive structure. The traditional chiral optical switch material mainly uses azobenzene, diarylethene and other molecular switches as photosensitive units, and adjusts and controls the reversible photoisomerization of the molecular switches through optical stimulation, so as to dynamically adjust and control Circularly Polarized Light (CPL) of the molecular switches, including but not limited to amplification, overturn and the like of chiral signals. But azobenzene generates cis-isomer in photoisomerization process, has thermal instability, and the obtained chiral optical switch has temporary property and poor stability, which greatly limits further application of the chiral optical switch molecule. And most of the existing hydrazone switch molecules cannot be subjected to photoinduction reversible isomerization in a solid state, which also influences the expansion application of the hydrazone switch molecules in the anti-counterfeiting encryption field.
Therefore, in order to widen the application field of the chiral optical switch material in the fields of photoelectric information storage and anti-counterfeiting, it is very necessary to develop a novel chiral optical switch molecule with long thermal half-life and high-efficiency reversible photoisomerization performance.
Disclosure of Invention
The invention aims to provide a hydrazone-based bistable chiral optical switch material, and preparation and application thereof, wherein the chiral optical switch material has photoinduction reversible isomerism properties in a solution state and a solid state, and provides a new thought and a new method for multiple anti-counterfeiting and information encryption.
The technical scheme of the invention is as follows:
The bistable chiral optical switch material based on hydrazone is prepared by taking a hydrazone molecular switch as a framework, introducing N, N-dimethylaniline as an electron donor at one end of the hydrazone molecular switch, modifying a benzene ring as an electron acceptor at the other end of the hydrazone molecular switch, and introducing a chiral center into an ester side chain, and the bistable chiral optical switch material is formed into a push-pull electron structure, wherein the structural formula of the chiral optical switch material is as follows:
Further, N, N-dimethylaniline is used as a rotor, a benzene ring is used as a stator, and a chiral center is matched, so that the chiral optical switch material is subjected to reversible photoisomerization under the irradiation of visible light with the wavelength of 440nm or 410nm and ultraviolet light with the wavelength of 340nm or 365nm, and simultaneously light emission is quenched and recovered; under the irradiation of visible light with the wavelength of 440nm or 410nm, the isomerization conversion of Z-E can be realized, and under the irradiation of light with the wavelength of 340nm or 365nm, the recovery of E-Z occurs.
Furthermore, the hydrazone-based bistable chiral optical switch material can be reversibly isomerized and circulated for ten times under the irradiation of visible light with the wavelength of 440nm and ultraviolet light with the wavelength of 340nm, and has good cycle reversibility.
Further, the synthetic route of the chiral optical switch material is as follows:
further, the preparation steps of the chiral optical switch material are as follows:
(1) Preparation of compound 2: dissolving 4-bromo-N, N-dimethylaniline in tetrahydrofuran, cooling to-78 ℃ under the protection of nitrogen, dropwise adding N-butyllithium, and stirring to obtain a suspension; adding diethyl oxalate into the suspension, stirring for reaction at-78 ℃, slowly heating to room temperature, adding water for quenching reaction, extracting, drying, and performing column chromatography after rotary evaporation to obtain a compound 2;
(2) Preparation of compound 3: dissolving the compound 2 and lithium hydroxide in a mixed solvent of water and ethanol, heating to 80 ℃ for reflux reaction, concentrating a reaction liquid, acidifying with dilute hydrochloric acid, precipitating solid, filtering and drying to obtain a yellow solid powdery compound 3;
(3) Preparation of Compound 4: dissolving a compound 3, N-dimethylaminopyridine and S- (-) -2-methyl-1-butanol in a dichloromethane solution, slowly adding the mixture into the dichloromethane solution of dicyclohexylcarbodiimide at 0 ℃, stirring the mixture at room temperature overnight, adding ethanol, washing filtrate with HCl with the mass concentration of 10% and a saturated NaHCO 3 solution, washing the filtrate with brine to be neutral, drying the washed filtrate, and performing silica gel column chromatography to obtain an orange oily compound 4;
(4) Preparation of hydrazone chiral switch molecule 1: under the nitrogen atmosphere, phenylhydrazine and acetic acid are added into ethanol solution of the compound 4, the temperature is raised to 80 ℃ for reflux reaction, the reaction is cooled to room temperature after the reaction is finished, ethanol is removed in vacuum, crude residues are dissolved in dichloromethane, and the compound 1 is obtained through washing, drying, decompression and solvent removal, and silica gel column chromatography purification.
The hydrazone-based bistable chiral optical switch material can be applied to the fields of information storage and multiple anti-counterfeiting, and circular polarization luminescence signals of the material can be effectively regulated and controlled under the solid state after optical stimulation, and the material has repeatability, specifically, Z-E isomerization conversion is realized under the irradiation of visible light with the wavelength of 440nm, and meanwhile, complete quenching of emission and existence of CPL signals are carried out; under the irradiation of visible light with the wavelength of 365nm, E-Z reversion conversion is realized, and simultaneously, the reversion of emission and the existence of CPL signals are accompanied.
Compared with the prior art, the invention has the following advantages:
1. The chiral optical switch material provided by the application takes the hydrazone molecular switch as a framework, N-dimethylaniline is introduced at one end of the chiral optical switch material as an electron donor, a benzene ring is modified at the other end of the chiral optical switch material as an electron acceptor, and the switch material with a push-pull electron structure can realize the conversion of photophysical properties under the irradiation of visible light/ultraviolet light under the condition that an ester side chain is introduced into a chiral center;
2. the hydrazone-based chiral optical switch material prepared by the application overcomes the defects of poor chemical stability, low ultraviolet excitation and light conversion efficiency, lack of solid conversion or fluorescence emission of some existing photochromic materials, and has the advantages of long thermal half-life, high stability, switchable solution/solid luminescence and the like;
3. The hydrazone-based chiral optical switch material disclosed by the application has the property of photoinduced reversible isomerism in a solid state, a circularly polarized light-emitting signal of the chiral optical switch material can be effectively regulated and controlled after light stimulation, the chiral optical switch material has repeatability, and an initial solid 1-Z has an obvious CPL signal to emit bright yellow light; under the irradiation of light with the wavelength of 440nm, the yellow light is quenched and simultaneously the CPL signal disappears; light irradiation at 365nm can cause the CPL signal to reappear, accompanied by weak yellow light; this characteristic of the material would be expected to provide a new and effective way for multiple anti-counterfeiting and information encryption applications;
4. The hydrazone-based chiral optical switch material disclosed by the application has the advantages of simple synthesis steps and considerable yield, and is suitable for large-scale production and application.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum (deuterated chloroform) of a chiral hydrazone switch molecule prepared in example one;
FIG. 2 is a schematic diagram of the reversible isomerization process and a comparative diagram of nuclear magnetism (deuterated toluene) before and after isomerization of the chiral hydrazone switch molecule prepared in example one;
FIG. 3 is an ultraviolet-visible absorption spectrum and a photoisomerization absorption cycle chart of the chiral hydrazone switch molecule solution prepared in example one before and after illumination;
FIG. 4 is a graph of ultraviolet visible emission spectrum and photoisomerization emission cycle of the chiral hydrazone switch molecule solution prepared in example one before and after illumination;
FIG. 5 is a graph showing the absorbance of a chiral hydrazone switch molecule solution prepared in example one as a function of irradiation time;
FIG. 6 is an Arrhenius diagram of the thermal isomerization of a chiral hydrazone switch molecule prepared in example one in toluene-d 8;
FIG. 7 is a graph showing the emission spectrum and emission cycle of solid powder of chiral hydrazone switch molecules prepared in example one before and after illumination;
FIG. 8 is a graph showing the circular polarized luminescence spectrum of the solid powder of the chiral hydrazone switch molecule prepared in example one before and after illumination.
Detailed Description
The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.
Embodiment one: preparation of chiral hydrazone switch molecule
The chemical structural formula is as follows
The specific synthetic route is as follows:
The specific synthesis steps are as follows:
(1) Preparation of compound 2: 4-bromo-N, N-dimethylaniline (3 g) was added to a 250mL reaction flask under nitrogen; 25mL of dry tetrahydrofuran is injected into the bottle, the reaction system is cooled to-78 ℃, 1.6M n-butyllithium (9.46 mL) is added dropwise, and the mixture is stirred for 15min to obtain a suspension; adding 3.26mL diethyl oxalate into a reaction bottle, stirring the mixed system at-78 ℃ for 20min, heating to room temperature, slowly adding 40mL of water, and quenching the reaction; the reaction solution was extracted with a large amount of water and methylene chloride, the organic layer was collected and dried, the organic solvent was removed by rotary evaporation, and then purified by column chromatography using petroleum ether and methylene chloride (20:100, v/v) as a eluent to give a bright yellow solid, yield: 67%.
1H NMR(400MHz,CDCl3)δ7.90(d,J＝9.2Hz,2H),6.66(d,J＝9.2Hz,2H),4.41(m,2H),3.10(s,6H),1.41(t,J＝7.2Hz,3H).
(2) Preparation of compound 3: compound 2 (500 mg) and lithium hydroxide (400 mg) were taken as solids in a flask, 30mL of water and 5mL of ethanol solution were added, and heated to 80 ℃ and refluxed for 2.5h; after the reaction is finished, concentrating the reaction liquid until precipitation is about to occur; acidify with diluted hydrochloric acid (hydrochloric acid and water 1:1) to ph=around 3.0. The solid precipitate is separated out, and the yellow solid powder is obtained by suction filtration and drying, and the yield is: 90%.
1H NMR(400MHz,CDCl3)δ8.48(d,J＝9.3Hz,2H),6.68(d,J＝9.4Hz,2H),3.15(s,6H)。
(3) Preparation of Compound 4: a solution of 386mg of Compound 3, 36.6mg of N, N-dimethylaminopyridine (4-DMAP), 88mg of S- (-) -2-methyl-1-butanol in dichloromethane (45 mL) was slowly added to a solution of dicyclohexylcarbodiimide (DCC, 309 mg) in dichloromethane (15 mL) at 0deg.C; stirring overnight at room temperature, adding ethanol (3 mL), washing the filtrate with 10% HCl and saturated NaHCO 3 solution, then washing with brine to neutrality; the mixture was dried over anhydrous Na 2SO4 and chromatographed on silica gel to give compound 4 as an orange oil.
1H NMR(400MHz,CDCl3)δ7.88(d,J＝8.8Hz,2H),6.67(d,J＝8.8Hz,2H),4.24(m,1H),4.15(m,1H),3.10(s,6H),1.85(m,1H),1.49(m,1H),1.23(m,1H),0.98(d,J＝6.7Hz,3H),0.93(t,J＝7.5Hz,3H).
(4) Preparation of Compound 1: 0.34mL of phenylhydrazine and a few drops of acetic acid (HOAc) were added to an ethanol solution (30 mL) of compound 4 (526 mg) under an N 2 atmosphere, heated to 80℃under reflux overnight, and then cooled to room temperature; the ethanol was removed in vacuo, the crude residue was dissolved in Dichloromethane (DCM), washed with water (30 mL), saturated sodium bicarbonate solution (30 mL) and brine (30 mL), then dried over anhydrous Na 2SO4, the solvent removed under reduced pressure, and the residue was chromatographed on silica gel to give a yellow solid, compound 1. Yield: 82%.
1H NMR(400MHz,CDCl3)δ12.19(s,1H),7.58(d,J＝8.9Hz,2H),7.33-7.28(m,2H),7.25(d,J＝7.0Hz,2H),6.95(t,J＝7.0Hz,1H),6.74(d,J＝8.9Hz,2H),4.19(m,1H),4.09(m,1H),3.00(s,6H),1.88-1.78(m,1H),1.47(m,1H),1.28-1.22(m,1H),0.98(d,J＝6.7Hz,3H),0.93(t,J＝7.5Hz,3H).13C NMR(100MHz,CDCl3)δ164.20(s),150.05,143.76,129.46,129.27,128.65,124.82,121.76,113.95,111.74,69.57,40.50,34.11,26.14,16.71,11.23.
Test example: characterization of chiral hydrazone switch molecules and photophysical property testing:
1. Chiral hydrazone switch molecules (5-10 mg) were dissolved in 0.5mL of deuterated chloroform and their structure was characterized by 400Hz nuclear magnetic resonance spectroscopy, figure 1 shows its nuclear magnetic resonance hydrogen spectrum, the compound exists mainly in the form of Z isomer.
2. The chiral hydrazone switch molecule can be isomerized by 410nm or 440nm light as shown in the small diagram (a) in fig. 2, and is converted into E from Z; light at 340nm or 365nm can return it, converting from E to Z. The nuclear magnetic resonance contrast diagram of the chiral hydrazone switch molecule before and after isomerism is shown in a small diagram (b) in fig. 2: i) Before light irradiation at 440 nm; ii) after light irradiation at 440 nm; iii) 1H NMR spectra after irradiation with light at 340nm reached photostable (deuterated toluene; the isomer ratio was determined by the H signal on the amino group), it is obvious that when the chiral hydrazone switch molecule was irradiated with 440nm visible light, the H on the amino group was shifted from the original 12.60ppm to the high field to 8.24ppm, and the CH 2 on the ester group was slightly shifted (4.01 ppm. Fwdarw.4.20 ppm), and the peaks around 12.60ppm and 4.01ppm were completely disappeared, indicating that the complete isomerism of Z.fwdarw.E was achieved under 440nm irradiation; peaks at 12.60ppm and 4.01ppm reappear under 340nm uv light, and calculation of peak areas before and after chemical shift indicates that e→z can be substantially recovered (E/z=83/17). This also confirms the schematic diagram of the isomerisation process shown in panel (a) of figure 2.
3. The toluene solution (1.0X10 -5 M) of the chiral hydrazone switch molecule was measured for the ultraviolet visible absorption spectrum and the photoisomerization absorption cycle graph before and after the irradiation, and the results are shown in panels (a) and (b) of FIG. 3, respectively. The absorbance change at 395nm was detected at room temperature under alternating irradiation of light at 440nm and 340nm, and the result is shown in (b) panel in fig. 3, from which it can be seen that the cycle of reversible isomerization was ten times under alternating irradiation of light at 440nm and 340nm, and absorption was not greatly lost, indicating that the chiral optical switch molecule had good cycle reversibility.
4. The toluene solution (1.0X10 -5 M) of the chiral hydrazone switch molecule was measured for its ultraviolet visible emission spectrum (λ ex =365 nm) and photoisomerization emission cycle profile before and after illumination, and the results are shown in panels (a) and (b) of FIG. 4, respectively. The change of the emission intensity at 520nm was detected under alternating irradiation of light at 440nm and 340nm at room temperature, and the result is shown in (b) panel in fig. 4, from which it can be seen that the cycle of reversible isomerization was ten times under alternating irradiation of light at 440nm and 340nm, without significant loss of emission, indicating that the chiral optical switch molecule has good cycle reversibility.
5. The photoisomerization quantum yield of the chiral hydrazone switch molecule in toluene solution was determined. As shown in panel (a) of fig. 5, the photoisomerization transition of the chiral hydrazone switch molecule from Z to E (irradiation wavelength 440 nm) occurs in toluene solution (1.0×10 -5 M) at room temperature, which is a graph of absorbance of Z (λ max =395 nm) as a function of irradiation time, and the resulting photoisomerization quantum yield Φ Z→E＝21.9±0.6％(εZ@440nm＝6400M-1·cm-1 is used for the calculation of quantum yield. As shown in panel (b) of fig. 5, photoisomerization (irradiation wavelength 340 nm) of the chiral hydrazone switch molecule from 1-E to 1-Z occurs in toluene solution (1.0x10 -5 M) at room temperature, and the absorbance of E (λ max =395 nm) is plotted as a function of irradiation time, and the resulting photoisomerization quantum yield Φ E→Z＝36.6±0.7％(εE@340nm＝18500M-1·cm-1 is used for calculation of quantum yield.
6. Arrhenius diagram of thermal isomerization of the chiral hydrazone switch molecule in toluene-d 8 was determined. The results are shown in FIG. 6, where the chiral hydrazone switch molecules exhibit bistable character. In deuterated toluene, under the irradiation of light with the wavelength of 440nm, the Z isomer is converted into the E isomer, the E isomer is placed in an oil bath at different temperatures, and the condition that the E thermal isomer returns to Z after different times is studied through a nuclear magnetic spectrum diagram, so that the thermal half life of the chiral hydrazone switch molecule at room temperature is calculated. The calculation result shows that the half-life of the chiral hydrazone switch molecule is about 15 years (1.30X10 5 h).
7. The solid powder of the chiral hydrazone switch molecule was measured for ultraviolet-visible emission spectra (λ ex =365 nm) and photoisomerization emission cycle graphs before and after illumination, and the results are shown in panels (a) and (b) of fig. 7, respectively. The change in the emission intensity at 520nm was detected under alternating irradiation of light at 440nm and 365nm at room temperature, and the result is shown in (b) panel in fig. 7, from which it can be seen that the reversible isomerization cycle was 5 times under alternating irradiation of light at 440nm and 365nm, indicating that the chiral optical switch molecule was completely isomerized and partially recovered in the solid state.
8. Measuring the circular polarization luminescence spectrum of the solid powder of the chiral hydrazone switch molecule before and after illumination; the results are shown in FIG. 8. The circular polarization luminescence spectra of (a) and (b) panels in FIG. 8 are those of 1-Z, the circular polarization luminescence spectra of (c) and (d) panels in FIG. 8 are those of 1-E, and the circular polarization luminescence spectra of (E) and (f) panels in FIG. 8 are those of 1-E reversibly isomerized back to 1-Z under light irradiation at 365nm wavelength.
As can be seen from fig. 8, in the solid state, the position of the maximum emission peak of the chiral hydrazone switch molecule 1-Z is around 520nm, and a recognizable CPL signal is detected, the CPL signal is close to 60mdeg, and the initial solid 1-Z emits bright yellow light; when irradiated with a 440nm visible light lamp, 1-Z can be converted to 1-E in the solid state, with quenching of the emission, yellow quenching, and CPL signal undetectable. When irradiated with ultraviolet light having a wavelength of 365nm, 1-E is partially converted into 1-Z, the maximum emission peak intensity is enhanced, and the position is slightly red shifted to 540nm, so that the CPL signal can be re-detected, and the CPL signal is close to 15mdeg along with weak yellow light. Furthermore, the asymmetry factor g lum at the maximum emission wavelength of 1-Z and @365nm is in the order of 10 -3. The result shows that the existence of CPL signals can be regulated and controlled by light control, and a new thought and method can be provided for multiple anti-counterfeiting and information encryption.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (3)
1. The application of the hydrazone-based bistable chiral optical switch material in the fields of information storage and multiple anti-counterfeiting is characterized in that the chiral optical switch material can regulate and control a circularly polarized luminous signal after being subjected to optical stimulation in a solid state and has repeatability; under the irradiation of visible light with the wavelength of 440nm, Z-E isomerization conversion is realized, and complete quenching of emission and existence of CPL signals are accompanied; under the irradiation of visible light with the wavelength of 365nm, E-Z reversion conversion is realized, and simultaneously, the reversion of emission and the existence of CPL signals are accompanied;
the hydrazone-based bistable chiral optical switch material is obtained by taking a hydrazone molecular switch as a framework, introducing N, N-dimethylaniline as an electron donor at one end of the hydrazone molecular switch, modifying a benzene ring as an electron acceptor at the other end of the hydrazone molecular switch, and introducing a chiral center into an ester side chain, wherein the structural formula of the chiral optical switch material is as follows:
2. The use of a hydrazone-based bistable chiral optical switching material in the fields of information storage and multiple anti-counterfeiting according to claim 1, wherein N, N-dimethylaniline is used as a rotor, a benzene ring is used as a stator, and a chiral center is matched, so that the chiral optical switching material is subjected to reversible photoisomerization under the irradiation of visible light with the wavelength of 440nm or 410nm and ultraviolet light with the wavelength of 340nm or 365nm, and is accompanied with quenching and recovery of luminescence; under the irradiation of visible light with the wavelength of 440nm or 410nm, the isomerization conversion of Z-E can be realized, and under the irradiation of light with the wavelength of 340nm or 365nm, the recovery of E-Z occurs.
3. The application of the hydrazone-based bistable chiral optical switch material in the fields of information storage and multiple anti-counterfeiting is characterized in that the chiral optical switch material can be reversibly isomerized and circulated for a plurality of times under the irradiation of visible light with the wavelength of 440nm and ultraviolet light with the wavelength of 340nm, and has good cycle reversibility.
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| Divergent Roles of Urea and Phosphoric Acid Derived Catalysts in Reactions of Diazo Compounds;Barbara Bernardim et al.;《Synthesis》;第48卷;677-686 * |
| On the Paternò–Büchi reaction of chiral phenylglyoxylate esters with furan derivatives;Maurizio D’Auria et al.;《Photochem. Photobiol. Sci.》;第2卷;904-913 * |
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