CN115108940A - Bistable chiral optical switch material based on hydrazone and preparation and application thereof - Google Patents
Bistable chiral optical switch material based on hydrazone and preparation and application thereof Download PDFInfo
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- 150000007857 hydrazones Chemical class 0.000 title claims abstract description 62
- 230000003287 optical effect Effects 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 20
- 238000007699 photoisomerization reaction Methods 0.000 claims abstract description 16
- 230000002441 reversible effect Effects 0.000 claims abstract description 16
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 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
- 230000010287 polarization Effects 0.000 claims abstract description 6
- 230000000638 stimulation Effects 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 229940126214 compound 3 Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- XYZWMVYYUIMRIZ-UHFFFAOYSA-N 4-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(Br)C=C1 XYZWMVYYUIMRIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 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 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- IGJDINDKLXPNKE-UHFFFAOYSA-N 1-N,3-N-dimethyl-2H-pyridine-1,3-diamine Chemical compound CNN1CC(=CC=C1)NC IGJDINDKLXPNKE-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000005286 illumination Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 239000006244 Medium Thermal Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012267 brine Substances 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- YXFVVABEGXRONW-UICOGKGYSA-N 1-deuterio-2-methylbenzene Chemical compound [2H]C1=CC=CC=C1C YXFVVABEGXRONW-UICOGKGYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 101100163901 Rattus norvegicus Asic2 gene Proteins 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 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
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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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- 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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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
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- 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
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- 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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Abstract
The invention discloses a bi-stable chiral optical switch material based on hydrazone, which is characterized in that a hydrazone molecular switch is used as a framework, N-dimethylaniline is introduced into one end of the hydrazone molecular switch to be used as an electron donor, a benzene ring modified from the other end of the hydrazone molecular switch to be used as an electron acceptor, and a chiral center is introduced into an ester side chain to obtain the bi-stable chiral optical switch material. In a solution state, the optical switch material with the push-pull electron structure can realize the conversion of the photophysical properties under the irradiation of visible light/ultraviolet light, and has good light-induced reversible isomerization characteristics; 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 light-induced reversible isomerism in a solid state, and a circular polarization luminescent signal of the chiral optical switch material can be effectively regulated and controlled after light stimulation, and the chiral optical switch material has repeatability, so that a new effective way can be provided 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 as well as preparation and application thereof.
Background
The chiral switch material has a wide potential application prospect in the fields of information storage, optical sensing, chiral biological imaging, anti-counterfeiting encryption and the like, and attracts the attention of technicians in the field. In recent years, many stimulus-responsive chiral switching materials have been developed, and chiral optical 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, the main preparation strategy of the chiral optical switch material is to modify a chiral center on a molecular optical switch as a photosensitive structure. The traditional chiral optical switch material mainly uses molecular switches such as azobenzene, diarylethene and the like as photosensitive units, and can dynamically regulate and control the Circular Polarized Light (CPL) of the molecular switches by regulating and controlling the reversible photoisomerization of the molecular switches through optical stimulation, wherein the steps include but are not limited to amplification, turning and the like of chiral signals. However, azobenzene generates cis-isomer in the photoisomerization process, so that the azobenzene has thermal instability, the property of the obtained chiral optical switch is temporary, and the stability is poor, so that the problem greatly limits the further application of the chiral optical switch molecule. Most of the existing hydrazone switch molecules cannot perform photoinduced reversible isomerization in a solid state, so that the expansion application of the hydrazone switch molecules in the field of anti-counterfeiting encryption is influenced.
Therefore, in order to broaden the application scenes of the chiral optical switch material in the fields of photoelectric information storage and anti-counterfeiting, it is necessary to develop a novel chiral optical switch molecule with a longer thermal half-life period and high-efficiency reversible photoisomerization performance.
Disclosure of Invention
The invention aims to provide a bi-stable chiral optical switch material based on hydrazone, and preparation and application thereof.
The technical scheme of the invention is as follows:
a bi-stable state chiral optical switch material based on hydrazone 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 to form a 'push-pull electron' structure, wherein the structural formula of the chiral optical switch material is as follows:
furthermore, 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 can generate 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, quenching and recovery of luminescence are accompanied; the isomerization conversion of Z → E can be realized under the irradiation of visible light with the wavelength of 440nm or 410nm, and the recovery of E → Z can be realized under the irradiation of light with the wavelength of 340nm or 365 nm.
Further, the hydrazone-based bistable chiral optical switch material can be subjected to reversible isomerization cycle 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 and reacting at-78 ℃, slowly heating to room temperature, adding water to quench and react, extracting, drying, performing rotary evaporation and performing column chromatography 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 the reaction solution, acidifying with dilute hydrochloric acid, precipitating a solid precipitate, and performing suction filtration and drying to obtain a yellow solid powdery compound 3;
(3) preparation of compound 4: dissolving compound 3, N-dimethylaminopyridine and S- (-) -2-methyl-1-butanol in dichloromethane solution, slowly adding the dichloromethane solution to dicyclohexylcarbodiimide solution at 0 ℃, stirring the dichloromethane solution at room temperature overnight, adding ethanol, and filtering the filtrate by using HCl with the mass concentration of 10% and saturated NaHCO 3 Washing the solution, washing the solution to be neutral by using saline, drying the solution, and carrying out silica gel column chromatography to obtain an orange oily compound 4;
(4) preparation of hydrazone chiral switch molecule 1: adding phenylhydrazine and acetic acid into an ethanol solution of the compound 4 under the nitrogen atmosphere, heating to 80 ℃ for reflux reaction, cooling to room temperature after the reaction is finished, removing ethanol in vacuum, dissolving crude residue in dichloromethane, washing, drying, removing a solvent under reduced pressure, and purifying by silica gel column chromatography to obtain the compound 1.
The bi-stable chiral optical switch material based on hydrazone can be applied to the fields of information storage and multiple anti-counterfeiting, and the material can effectively regulate and control the circular polarization luminescent signal after optical stimulation in a solid state and has repeatability, particularly, under the irradiation of visible light with the wavelength of 440nm, the Z → E isomerization transformation is realized, and simultaneously, the complete quenching of emission and the existence to the absence of a CPL signal are accompanied; under 365nm visible light irradiation, the E → Z reversion transition is achieved with concomitant reversion of the emission and CPL signal from absent to present.
Compared with the prior art, the invention has the following advantages:
1. the chiral optical switch material provided by the application takes a hydrazone molecular switch as a framework, N-dimethylaniline is introduced into 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 material as an electron acceptor, a chiral center is introduced into an ester side chain, 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 in a solution state;
2. the hydrazone-based chiral optical switch material prepared by the application overcomes the defects of poor chemical stability, low ultraviolet light excitation, low light conversion efficiency and lack of solid conversion or fluorescence emission of some existing photochromic materials, and has the advantages of long thermal half-life period, 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 photoinduction reversible isomerism in a solid state, a circular polarization luminescent signal can be effectively regulated and controlled after optical stimulation, and the material has repeatability, and an initial solid 1-Z has an obvious CPL signal and emits bright yellow light; under the irradiation of light with the wavelength of 440nm, the yellow light is quenched and simultaneously disappears along with the CPL signal; light irradiation at 365nm can cause the CPL signal to reappear with faint yellow light; the characteristic of the material is expected to provide a new 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 synthetic 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 the chiral hydrazone switch molecule prepared in example one;
FIG. 2 is a schematic diagram of the reversible isomerization process and nuclear magnetic comparison before and after isomerization (deuterated toluene) of the chiral hydrazone switch molecule prepared in example one;
FIG. 3 is a graph of the UV-VIS absorption spectrum and the photoisomerization absorption cycle of the chiral hydrazone switch molecule solution prepared in example one before and after illumination;
FIG. 4 is a graph of the UV-VIS emission spectrum and the photoisomerization emission cycle of the chiral hydrazone switch molecule solution prepared in example one before and after illumination;
FIG. 5 is a graph of absorbance versus irradiation time for a solution of chiral hydrazone switch molecules prepared in example one;
FIG. 6 shows the chiral hydrazone switch molecule prepared in example one at toluene-d 8 Arrhenius plots of medium thermal isomerization;
FIG. 7 is a graph of the emission spectrum and the emission cycle of a solid powder of chiral hydrazone switch molecule prepared in example one before and after illumination;
fig. 8 is a circular polarization luminescence spectrum of solid powder of chiral hydrazone switch molecule prepared in example one before and after illumination.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The first embodiment is as follows: 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: adding 4-bromo-N, N-dimethylaniline (3g) into a 250mL reaction bottle under the protection of nitrogen; injecting 25mL of dry tetrahydrofuran into the bottle, cooling the reaction system to-78 ℃, dropwise adding 1.6M n-butyl lithium (9.46mL), and stirring for 15min to obtain a suspension; adding 3.26mL of 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 dichloromethane, 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 dichloromethane (20:100, v/v) as a washing agent to give a bright yellow solid, yield: 67%.
1H NMR(400MHz,CDCl 3 )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: taking compound 2(500mg) and lithium hydroxide (400mg) as solids, adding 30mL of water and 5mL of ethanol solution, and heating to 80 ℃ for refluxing for 2.5 h; after the reaction is finished, concentrating the reaction solution until the precipitation is about to appear; it was acidified with dilute hydrochloric acid (hydrochloric acid and water 1:1) to a pH of about 3.0. Precipitating a solid precipitate, filtering and drying to obtain yellow solid powder, wherein the yield is as follows: 90 percent.
1H NMR(400MHz,CDCl 3 )δ8.48(d,J＝9.3Hz,2H),6.68(d,J＝9.4Hz,2H),3.15(s,6H)。
(3) Preparation of compound 4: 386mg of compound 3, 36.6mg of N, N-dimethylaminopyridine (4-DMAP), 88mg of S- (-) -2-methyl-1-butanol in dichloromethane (45mL) was added slowly to a solution of dicyclohexylcarbodiimide (DCC, 309mg) in dichloromethane (15mL) at 0 ℃; stir at room temperature overnight, add ethanol (3mL), filtrate with 10% HCl and saturated NaHCO 3 Washing with the solution, and then washing with brine to neutrality; the mixture is mixed with anhydrous Na 2 SO 4 Drying and silica gel column chromatography gave compound 4 as an orange oil.
1H NMR(400MHz,CDCl 3 )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: in N 2 0.34mL of phenylhydrazine and a few drops of acetic acid (HOAc) were added to an ethanol solution (30mL) of Compound 4(526mg) under an atmosphere, heated to 80 ℃ for reflux overnight, and then cooled to room temperature; the ethanol was removed in vacuo and the crude residue was dissolved in Dichloromethane (DCM), washed with water (30mL), saturated sodium bicarbonate solution (30mL) and brine (30mL), then anhydrous Na 2 SO 4 Drying, removing solvent under reduced pressure, and performing silica gel column chromatography on the residue to obtain yellow solid, i.e. the compound 1. Yield: 82 percent.
1H NMR(400MHz,CDCl 3 )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,CDCl 3 )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 and photophysical property testing of chiral hydrazone switch molecules:
1. the chiral hydrazone switch molecule (5-10mg) is dissolved in 0.5mL of deuterated chloroform, the structure of the chiral hydrazone switch molecule is characterized by a 400Hz nuclear magnetic resonance instrument, and a nuclear magnetic resonance hydrogen spectrogram of the chiral hydrazone switch molecule is shown in figure 1, wherein the compound mainly exists in a Z isomer form.
2. The chiral hydrazone switch molecule reversible isomerization process is schematically shown in a small graph (a) in fig. 2, light of 410nm or 440nm can cause the chiral hydrazone switch molecule to be isomerized, and the chiral hydrazone switch molecule reversible isomerization process is converted from Z to E; light at 340nm or 365nm can cause it to revert from E to Z. The nuclear magnetism comparison graph before and after the chiral hydrazone switch molecule isomerization is shown as a small graph (b) in figure 2: i) before irradiation with light of 440 nm; ii) after irradiation with light at 440 nm; iii) 1H NMR spectrum to reach a photostable state after 340nm light irradiation (deuterotoluene; using the signal of H on the amino group to determine the isomer ratio), it can be clearly seen that when the chiral hydrazone switch molecule is irradiated under 440nm visible light, the H on the amino group will move from the original 12.60ppm to the high field to 8.24ppm, and the CH on the ester group 2 There was also a weak shift (4.01ppm → 4.20ppm) and the peaks near 12.60ppm and 4.01ppm disappeared completely, indicating that complete isomerism of Z → E can be achieved under 440nm irradiation; when irradiated under ultraviolet light at 340nm, peaks at 12.60ppm and 4.01ppm reappear, and calculation of the peak areas before and after chemical shift indicates that E → Z can substantially recover (E/Z-83/17). This also confirms the schematic isomerization process shown in fig. 2 (a) panel.
3. The chiral hydrazone switch molecule was assayed in toluene (1.0X 10) -5 M) ultraviolet-visible absorption spectrum graph and photoisomerization absorption cycle graph before and after illumination, and the results are respectively shown in (a) and (b) panels in FIG. 3. The change in absorbance at 395nm under the alternate irradiation of light with the wavelengths of 440nm and 340nm at room temperature was detected, and the result is shown in (b) small graph in FIG. 3, from which it can be seen that light with the wavelengths of 440nm and 340nm alternateUnder irradiation, reversible isomerization cycle can be performed for ten times, and absorption has no large loss, which indicates that the chiral optical switch molecule has good cycle reversibility.
4. The chiral hydrazone switch molecule was assayed in toluene (1.0X 10) -5 M) ultraviolet visible emission spectra before and after illumination (lambda) ex 365nm) and photoisomerization emission cycle plots, the results are shown in panels (a) and (b) of fig. 4, respectively. At room temperature, under the alternate irradiation of light with the wavelengths of 440nm and 340nm, the change of the emission intensity at 520nm is detected, and the result is shown in a small graph (b) in fig. 4, and it can be seen from the graph that under the alternate irradiation of light with the wavelengths of 440nm and 340nm, the reversible isomerization cycle can be performed ten times, and the emission has no large-amplitude loss, which indicates that the chiral optical switch molecule has good cycle reversibility.
5. And measuring the photoisomerization quantum yield of the chiral hydrazone switch molecule in the toluene solution. As shown in the panel (a) of FIG. 5, at room temperature, a toluene solution (1.0X 10) -5 M) the chiral hydrazone switch molecule undergoes photoisomerization conversion from Z to E (irradiation wavelength 440nm), and the figure shows the absorbance of Z (lambda) max 395nm) as a function of irradiation time, the resulting photoisomerization quantum yield was Φ Z→E ＝21.9±0.6％(ε Z@440nm ＝6400M -1 ·cm -1 Used for quantum yield calculations). As shown in the panel (b) of FIG. 5, at room temperature, the toluene solution (1.0X 10) -5 M) the chiral hydrazone switch molecule undergoes photoisomerization (irradiation wavelength is 340nm) from 1-E to 1-Z, and the figure shows the absorbance (lambda) of E max 395nm) as a function of irradiation time, the resulting photoisomerization quantum yield was Φ E→Z ＝36.6±0.7％(ε E@340nm ＝18500M -1 ·cm -1 Used for quantum yield calculations).
6. Determining the chiral hydrazone switch molecule in toluene-d 8 Arrhenius pattern of medium thermal isomerization. As a result, the chiral hydrazone switch molecule exhibits a bistable character, as shown in FIG. 6. 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 under oil bath pots with different temperatures, and the thermal isomerization of the E is carried out back after different times of research through nuclear magnetic spectrumAnd returning to the condition of Z, thereby calculating the thermal half-life of the chiral hydrazone switch molecule at room temperature. The calculation result shows that the half-life period of the chiral hydrazone switch molecule is as long as about 15 years (1.30 multiplied by 10) 5 h)。
7. Measuring the ultraviolet visible emission spectrogram (lambda) of the solid powder of the chiral hydrazone switch molecule before and after illumination ex 365nm) and photoisomerization emission cycle plots, the results are shown in fig. 7, panels (a) and (b), respectively. At room temperature, under the alternate irradiation of light with the wavelengths of 440nm and 365nm, the change of the emission intensity at 520nm is detected, and the result is shown in a small graph (b) in fig. 7, and from the graph, the reversible isomerization cycle can be realized for 5 times under the alternate irradiation of the light with the wavelengths of 440nm and 365nm, which shows that the chiral optical switch molecule can be completely isomerized and partially recovered under 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 plots in FIG. 8 (a) and (b) are plots of 1-Z circular polarized luminescence, the plots in FIG. 8 (c) and (d) are plots of 1-E circular polarized luminescence, and the plots in FIG. 8 (E) and (f) are plots of 1-E circular polarized luminescence reversibly photoisomerized back to 1-Z under 365nm light.
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 distinguishable CPL signal is detected, the CPL signal is close to 60mdeg, and the initial solid 1-Z emits bright yellow light; when the light is irradiated by a 440nm visible light lamp, 1-Z can be converted to 1-E in a solid state, and simultaneously, the emission is quenched, yellow light is quenched, and CPL signals cannot be detected. When irradiated with 365nm UV light, the 1-E shifts to 1-Z, with an increase in the intensity of the maximum emission peak and a slight red shift in position to 540nm, and the CPL signal is re-detected and accompanied by a faint yellow light, approaching 15 mdeg. Furthermore, the asymmetry factor g at the maximum emission wavelengths of 1-Z and @365nm lum Are all at 10 -3 An order of magnitude. The results show that the CPL signal can be controlled by light control, so that a new idea and a new method can be provided for multiple anti-counterfeiting and information encryption.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (6)
1. The bi-stable chiral optical switch material based on hydrazone is characterized in that a hydrazone molecular switch is used as a framework, N-dimethylaniline is introduced into one end of the hydrazone molecular switch to be used as an electron donor, a benzene ring is modified at the other end of the hydrazone molecular switch to be used as an electron acceptor, and a chiral center is introduced into an ester side chain, so that the structural formula of the chiral optical switch material is as follows:
2. the bi-stable chiral hydrazone-based optical switching material as claimed in 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 undergoes reversible photoisomerization under irradiation of visible light with a wavelength of 440nm or 410nm and ultraviolet light with a wavelength of 340nm or 365nm, accompanied with quenching and recovery of luminescence; the isomerization conversion of Z → E can be realized under the irradiation of visible light with the wavelength of 440nm or 410nm, and the recovery of E → Z can be realized under the irradiation of light with the wavelength of 340nm or 365 nm.
3. The hydrazone-based bistable chiral optical switch material of claim 1, wherein the chiral optical switch material is capable of reversible isomerization cycles several times under irradiation of visible light with a wavelength of 440nm and ultraviolet light with a wavelength of 340nm, and has good cycle reversibility.
4. The method for preparing a hydrazone-based bistable chiral optical switch material as claimed in any one of claims 1 to 3, wherein the synthetic route is as follows:
5. the method of claim 4, wherein the method comprises the following steps:
(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 and reacting at-78 ℃, slowly heating to room temperature, adding water to quench and react, extracting, drying, performing rotary evaporation and performing column chromatography 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 the reaction solution, acidifying with dilute hydrochloric acid, precipitating a solid precipitate, and performing suction filtration and drying to obtain a yellow solid powdery compound 3;
(3) preparation of compound 4: dissolving compound 3, N-dimethylaminopyridine and S- (-) -2-methyl-1-butanol in dichloromethane solution, slowly adding the dichloromethane solution to dicyclohexylcarbodiimide solution at 0 ℃, stirring the dichloromethane solution at room temperature overnight, adding ethanol, and filtering the filtrate by using HCl with the mass concentration of 10% and saturated NaHCO 3 Washing the solution, washing the solution to be neutral by using saline, drying the solution, and carrying out silica gel column chromatography to obtain an orange oily compound 4;
(4) preparation of hydrazone chiral switch molecule 1: adding phenylhydrazine and acetic acid into an ethanol solution of the compound 4 under the nitrogen atmosphere, heating to 80 ℃ for reflux reaction, cooling to room temperature after the reaction is finished, removing ethanol in vacuum, dissolving crude residue in dichloromethane, washing, drying, removing a solvent under reduced pressure, and purifying by silica gel column chromatography to obtain the compound 1.
6. The application of the hydrazone-based bistable chiral optical switch material in the fields of information storage and multiple anti-counterfeiting as claimed in any one of claims 1 to 3, wherein the chiral optical switch material is in a solid state, and a circular polarization luminescence signal of the chiral optical switch material can be regulated and controlled after optical stimulation, and has repeatability; in particular, under irradiation with visible light at a wavelength of 440nm, the Z → E isomerization transition is achieved, accompanied by complete quenching of the emission and the presence to absence of the CPL signal; under 365nm wavelength visible light irradiation, the E → Z reversion transition is achieved with concomitant reversion of the emission and the CPL signal from absent to present.
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| US20210079134A1 (en) * | 2019-09-13 | 2021-03-18 | Trustees Of Dartmouth College | Polymer glass transition temperature manipulation via z/e hydrazone photoswitching |
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| US20210079134A1 (en) * | 2019-09-13 | 2021-03-18 | Trustees Of Dartmouth College | Polymer glass transition temperature manipulation via z/e hydrazone photoswitching |
Non-Patent Citations (5)
| Title |
|---|
| BAIHAO SHAO ET AL.: "Solution and Solid-State Emission Toggling of a Photochromic Hydrazone", 《J. AM. CHEM.》, vol. 140, pages 12323 - 12327, XP055670638, DOI: 10.1021/jacs.8b07108 * |
| BAIHAO SHAO ET AL.: "Solution and Solid-State Emission Toggling of a Photochromic Hydrazone-SI", 《J. AM. CHEM.》, vol. 140, pages 12323 - 12327, XP055670638, DOI: 10.1021/jacs.8b07108 * |
| BARBARA BERNARDIM ET AL.: "Divergent Roles of Urea and Phosphoric Acid Derived Catalysts in Reactions of Diazo Compounds", 《SYNTHESIS》, vol. 48, pages 677 - 686 * |
| HARUKI INADA ET AL.: "Synthesis of Unprotected 2‑Arylglycines by Transamination of Arylglyoxylic Acids with 2‑(2-Chlorophenyl)glycine", 《J. ORG. CHEM.》, vol. 85, pages 11047 - 11059 * |
| MAURIZIO D’AURIA ET AL.: "On the Paternò–Büchi reaction of chiral phenylglyoxylate esters with furan derivatives", 《PHOTOCHEM. PHOTOBIOL. SCI.》, vol. 2, pages 904 - 913 * |
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