CN107522688A - The class photochromic material of triaryl-ethylene containing thiophene derivant and its synthetic method and application - Google Patents
The class photochromic material of triaryl-ethylene containing thiophene derivant and its synthetic method and application Download PDFInfo
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- CN107522688A CN107522688A CN201710729448.0A CN201710729448A CN107522688A CN 107522688 A CN107522688 A CN 107522688A CN 201710729448 A CN201710729448 A CN 201710729448A CN 107522688 A CN107522688 A CN 107522688A
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- photochromic material
- triaryl
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- thiophene derivant
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 47
- 229930192474 thiophene Natural products 0.000 title claims abstract description 31
- 241001597008 Nomeidae Species 0.000 title claims abstract description 23
- 239000005977 Ethylene Substances 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 9
- -1 nitro, carboxyl Chemical group 0.000 claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 5
- 150000008366 benzophenones Chemical class 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000950 dibromo group Chemical group Br* 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012876 topography Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- MKYQPGPNVYRMHI-UHFFFAOYSA-N Triphenylethylene Chemical group C=1C=CC=CC=1C=C(C=1C=CC=CC=1)C1=CC=CC=C1 MKYQPGPNVYRMHI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IWHJPYXAFGKABF-UHFFFAOYSA-N 1,1-dibromoethene Chemical class BrC(Br)=C IWHJPYXAFGKABF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000005055 memory storage Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FWUHUNUOUDQTFG-UHFFFAOYSA-N (3,4,5-trifluorophenoxy)boronic acid Chemical class OB(O)OC1=CC(F)=C(F)C(F)=C1 FWUHUNUOUDQTFG-UHFFFAOYSA-N 0.000 description 1
- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical class OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
- A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
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- 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
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
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- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
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- Veterinary Medicine (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of class photochromic material of triaryl-ethylene containing thiophene derivant and its synthetic method and application, and thiophene derivant is introduced into triaryl-ethylene class photochromic material.Photochromic material stability of the invention is good, fast response time, can be in quick response under illumination condition, realize light-operated interface in real time and with good information store function and outstanding erasable property, reversible pattern change in real time is presented under 365nm/ visible ray illumination, and, synthetic method craft is simple, and products obtained therefrom easily purifies.The photochromic material of the present invention is applied to the fields such as light-operated switch, chemical-biological detection, optical information storage, in addition, due to it, photochromism occurs, material surface topography itself changes therewith simultaneously, therefore applies also for light-operated interface, false proof and wearable device etc..The present invention considerable yield, the cheap raw material being easy to get and gentle synthesis condition will also assign bigger market potential.
Description
Technical field
The present invention relates to the class photochromic material of triaryl-ethylene containing thiophene derivant and its synthetic method and in light-operated material
Material, the application of optical information storage.
Background technology
Photochromic material refers to after by light source activation, reversible physically or chemically change can occur, so as to which face occur
The material of color and other change in physical.(Bouas-Laurent H,Dürr H.Organic photochromism
(IUPAC technical report)[J].Pure and Applied Chemistry,2001,73(4):639-665.) light
Cause metachromatism to occur in inorganic and organic compound, photochromic compoundses because its structure determination, easily modification,
The features such as fatigue resistance is good is increasingly becoming the main study subject of photochromic material.(Minkin V I.Photo-,
thermo-,solvato-,and electrochromic spiroheterocyclic compounds[J].Chemical
Reviews,2004,104(5):2751-2776.) organic photochromic material mainly have it is following several：Spiro-pyrans class, Luo oxazines
Class, benzo pyran, azo, fulgides, triphenylmethane, diaryl ethylene compounds.But the organic light of tradition
Off-color material is caused the problems such as design synthesis is complicated, material cost is high, oxidizable and cycle-index is poor to be mostly present.
Triphenylethylene class photochromic material synthetic route is simple, photochromic properties are excellent, is that one kind has potential answer
With the photochromic material of value.Ou etc. is had by introducing contraposition chlorine atom on two phenyl ring of triphenylethylene homonymy
The triphenylethylene derivatives of excellent photochromic properties.(Ou D,Yu T,Yang Z,et al.Combined aggregation
induced emission(AIE),photochromism and photoresponsive wettability in simple
dichloro-substituted triphenylethylene derivatives[J].Chemical Science,2016,7
(8):5302.), however this kind of brand-new material cyclization state labile, recover automatically after ultraviolet irradiation is stopped.Therefore this is
In memory storage and in real time, the field such as light-operated interface still has some defects to row material, is further improved.
The content of the invention
It is an object of the invention to provide a kind of class photochromic material of triaryl-ethylene containing thiophene derivant, it can Real-Time Optical
Control, the quick response with good memory storage function and excellent erasable property.
It is a further object to provide the conjunction of the above-mentioned class of triaryl-ethylene containing thiophene derivant photochromic material
Into method, this method technique is simple, and yield is high, is easy to purify, and can adjust end-product by introducing different functional groups
The performances such as photochromic, emission wavelength.
Third object of the present invention is to be applied to the above-mentioned class of triaryl-ethylene containing thiophene derivant photochromic material
The fields such as light-operated interface, false proof, optical information storage, chemical-biological detection and wearable device.
The object of the present invention is achieved like this：A kind of class photochromic material of triaryl-ethylene containing thiophene derivant, its
Shown in general molecular formula such as formula (1)：
Formula (1)：
Wherein, R0For thiophene or derivatives thereof, R1And R2It is identical or different, selected from aromatic rings or derivatives thereof.
R0To be selected from following structure during thiophene or derivatives thereof：
R in its structure4、R5And R6It is identical or different, R4、R5And R6Selected from hydrogen, alkyl, halogen, alkoxy, nitro, carboxyl,
Amino, aldehyde radical or cyano group.
R1And R2To be selected from following structure during aromatic rings or derivatives thereof：
Wherein R7、R8And R9It is identical or different, R7、R8And R9Selected from hydrogen, alkyl, halogen, alkoxy, nitro, carboxyl, ammonia
Base, aldehyde radical or cyano group.
The synthetic method of the above-mentioned class of triaryl-ethylene containing thiophene derivant photochromic material, it is characterised in that：
(1) aromatic rings that formaldehyde substituent is contained in one end, heteroaromatic or derivatives thereof are reacted by Corey-Funchs
Synthesize its dibromo substituent；Pass through again with the aromatic compound containing boric acid or pinacol boric acid ester group or heterocyclic compound
Suzuki reacts to obtain target product；Or (2) by benzophenone derivative and the aromatic compound containing p diethylaminobenzoic acid ester group or
Heterocyclic compound reaction obtains target product by witig reaction.
The described class photochromic material of triaryl-ethylene containing thiophene derivant is preparing light control materials, optical information storage
Application in part, wearable device, chemical-biological detection product, bio-imaging product, anti-fake product.
The present invention's introduces triaryl-ethylene class photochromic material by thiophene derivant.Because thiophene derivant has more
Good conjugacy, can effectively stablize it is photochromic during cyclization state, therefore such photochromic material can be in light
The quick response according under the conditions of, realize light-operated interface in real time and with good information store function and outstanding erasable property,
Reversible pattern change in real time is presented under 365nm/ visible ray illumination.Moreover, synthetic method craft is simple, products obtained therefrom is easily pure
Change, synthesized photochromic material stability is good, fast response time, excellent erasable property.The photochromic material of the present invention
Material is suitable for fields such as light-operated switch, chemical-biological detection, optical information storages, further, since photochromism is occurring in it
Material surface topography itself changes therewith simultaneously, therefore applies also for light-operated interface, false proof and wearable device etc..This
To also bigger market potential be assigned by inventing considerable yield, the cheap raw material being easy to get and gentle synthesis condition.
In order to further illustrate the feature of the present invention and technology contents, the accompanying drawing below in connection with the present invention is referred to,
But accompanying drawing is only to provide reference and explanation, is not intended to be any limitation as the present invention.
Brief description of the drawings
Below in conjunction with the accompanying drawings, the embodiment of the present invention is described in detail, more clearly to express the present invention's
Technical scheme and other beneficial effects.
Fig. 1 is the photochromic front and rear contrast picture of the solution of the product of the embodiment of the present invention 2 and its ultraviolet-visible reflective spectrum
Comparison diagram, wherein, left side test tube be solution it is photochromic before, the right test tube be solution it is photochromic after send yellow-green fluorescence；
Fig. 2 is the photochromic front and rear contrast picture of the powder of the product of the embodiment of the present invention 2 and its ultraviolet-visible reflective spectrum
Comparison diagram, wherein, left side powder is before photochromic, and the right powder is sends yellow-green fluorescence after photochromic；
Fig. 3 is the photochromic front and rear ultraviolet-visible reflective spectrum comparison diagram of the powder of the product of the embodiment of the present invention 3.
Embodiment
The class photochromic material of triaryl-ethylene containing thiophene derivant of the present invention, shown in its general molecular formula such as formula (1)：
Formula (1)：
Wherein, R0For thiophene or derivatives thereof.R0To be selected from following structure during thiophene or derivatives thereof：
R in its structure4、R5And R6Can be with identical, can also be different, R4、R5And R6Can be hydrogen, alkyl, halogen, alcoxyl
Base, nitro, carboxyl, amino, aldehyde radical or cyano group.
R in formula (1)1Can be with R2It is identical, can also be different, R1And R2It can be aromatic rings or derivatives thereof.Wherein R1
And R2To be selected from following structure during aromatic rings or derivatives thereof：
R in its structure7、R8And R9Can be with identical, can also be different, R7、R8And R9Can be hydrogen, alkyl, halogen, alcoxyl
Base, nitro, carboxyl, amino, aldehyde radical or cyano group.
The synthetic method of the above-mentioned class of triaryl-ethylene containing thiophene derivant photochromic material：
Aromatic rings that formaldehyde substituent is contained in one end, heteroaromatic or derivatives thereof are passed through Corey-Funchs by method (1)
Reaction synthesizes its dibromo substituent；Pass through again with the aromatic compound containing boric acid or pinacol boric acid ester group or heterocyclic compound
Suzuki reacts to obtain target product.Specifically, including following sequential steps：1. provide the fragrance that formaldehyde substituent is contained in one end
Ring, heteroaromatic or derivatives thereof, in dichloromethane solution, under triphenylphosphine and carbon tetrabromide effect, normal-temperature reaction obtains
Its dibromo substituent；2. by foregoing dibromo substituent and the aromatic compound containing boric acid or pinacol boric acid ester group or jeterocyclic chemistry
Compound under potassium carbonate effect, is catalyzed to obtain target product in tetrahydrofuran solution by tetra-triphenylphosphine palladium.
Or method (2) is by benzophenone derivative and aromatic compound or heterocyclic compound containing p diethylaminobenzoic acid ester group
Reaction obtains target product by witig reaction.Specifically, there is provided benzophenone derivative and the virtue containing p diethylaminobenzoic acid ester group
Aroma compounds or heterocyclic compound obtain target production under potassium tert-butoxide effect in tetrahydrofuran solution by witig reaction
Thing.
The synthetic method craft of the present invention is simple, easily purifying, and synthesized photochromic material has stronger stability
With high response speed and good erasable property, the fields such as light-operated switch, chemical-biological detection, optical information storage are applicable.This
Outside, material reversible pattern in real time is presented under 365nm/ visible ray illumination changed in the present invention, suitable for light-operated interface, it is false proof and
The fields such as wearable device.
Below by way of specific examples of the implementation, the invention will be further elaborated, but the present invention is not limited thereto particular case
Son.
Embodiment 1
(1) intermediate【2- (2,2- dibromoethylenes) thiophene】Synthesis
60ml dichloromethane, 4.76g carbon tetrabromides (20mmol) and 10.49g triphenylphosphines are added in 250ml single-necked flasks
(40mmol), is positioned in ice-water bath, adds 1.12 grams of 2 thiophene carboxaldehydes (10mmol) after 1h is reacted on magnetic stirring apparatus, often
Temperature reaction 16h.Claret solution is obtained, steams excessive solvent in Rotary Evaporators, obtains oily mix products.Then utilize
The method of silica gel column chromatography is purified, and leacheate is n-hexane.Obtain white solid 1.88g, yield 70.15%.
(2) synthesis of target product
1.34g 2- (2,2- dibromoethylenes) thiophene (5mmol) and 1.68g phenyl boric acids are added in 250mL there-necked flasks
(15mmol), appropriate THF is added in nitrogen environment, add 3.45g K2CO3The 2mol/L aqueous solution that (15.00mmol) is made into,
Add 5 ‰ catalyst Pd (PPh3)4.Backflow is warming up on magnetic stirring apparatus, reacts 12h.Reaction solution is cooled down afterwards, added
Dichloromethane and water extraction, are extracted 3 times with dichloromethane, are washed with water 3 times.By organic layer anhydrous sodium sulfate drying, revolving
Turn to be spin-dried in evaporimeter.Then purified using the method for silica gel column chromatography, leacheate is n-hexane.Obtain white product
0.68g, yield 51.91%.1H NMR (500MHz, Chloroform-d) δ 7.47 (t, J=7.8Hz, 3H), 7.34 (d, J=
7.3Hz, 2H), 7.32-7.27 (m, 5H), 7.25 (s, 1H), 7.04 (d, J=5.0Hz, 1H), 6.93 (d, J=3.5Hz, 1H),
6.87 (dd, J=4.9,3.7Hz, 1H)
Embodiment 2
(2) synthesize target product, yield 76.42% using 4- fluorobenzoic boric acids for phenyl boric acid with reference to the step of embodiment 1.1H
NMR(500MHz,DMSO-d6) δ 7.49 (s, 1H), 7.38-7.28 (m, 5H), 7.25 (dd, J=8.4,5.7Hz, 2H), 7.16
(t, J=8.8Hz, 2H), 7.13 (d, J=3.4Hz, 1H), 6.93 (dd, J=5.0,3.7Hz, 1H)
Embodiment 3
(2) synthesize target product, yield 75.73% using 4- chlorophenylboronic acids for phenyl boric acid with reference to the step of embodiment 1.1H
NMR(400MHz,DMSO-d6) δ 7.60 (d, J=8.7Hz, 3H), 7.45-7.29 (m, 5H), 7.26 (d, J=8.3Hz, 2H),
7.18 (d, J=3.1Hz, 1H), 6.97 (dd, J=5.0,3.6Hz, 1H)
Embodiment 4
(2) synthesize target product, yield 68.36% using 2- naphthalenes phenyl boric acid for phenyl boric acid with reference to the step of embodiment 1
。1H NMR (500MHz, Chloroform-d) δ 8.70 (d, J=8.3Hz, 1H), 8.09 (d, J=8.4Hz, 1H), 7.92 (dd,
J=15.7,7.9Hz, 4H), 7.75 (d, J=8.0Hz, 1H), 7.61-7.49 (m, 6H), 7.45 (d, J=7.9Hz, 1H),
7.39-7.27 (m, 5H), 6.96 (d, J=5.1Hz, 1H), 6.90 (d, J=3.2Hz, 1H), 6.82 (dd, J=5.0,3.7Hz,
1H).
Embodiment 5
(2) replace phenyl boric acid synthesis target product using 3,4,5- trifluoro phenyl boric acids with reference to the step of embodiment 1, and yield is
78.94%.1H NMR (400MHz, Chloroform-d) δ 7.22 (s, 1H), 7.20 (d, J=5.0Hz, 1H), 6.95 (dd, J
=5.1,3.7Hz, 1H), 6.93-6.85 (m, 4H)
Table 1:Maximum emission wavelength of the end-product in solid, maximal ultraviolet-visible reflectance wavelength in embodiment
Note：After solid sample powder irradiates 10s under 365nm LED uviol lamps, by Shimadzu RF-5301PC fluorescence
The emission spectrum of spectrophotometer measurement solid；The Ocean Optic with Ocean Optic Maya2000PRO spectrometers
R600-125F reflection probes determine the ultraviolet-visible reflective spectrum of solid.
In summary, have the present invention relates to the class photochromic material of triaryl-ethylene containing thiophene derivant excellent photic
Discoloration and good erasable property, it is suitable for the fields such as light-operated switch, chemical-biological detection, optical information storage.In addition,
Reversible pattern change in real time is presented in material under 365nm/ visible ray illumination in the present invention, suitable for light-operated interface, false proof and can
Dress the fields such as device.Described above, one of ordinary skill in the art can be with technique according to the invention scheme and technology structure
Think of makes other various corresponding changes and deformation, and all these changes and deformation should all belong to the guarantor of the claims in the present invention
Protect scope.
Claims (7)
- A kind of 1. class photochromic material of triaryl-ethylene containing thiophene derivant, it is characterised in that general molecular formula such as formula (1) institute Show：Formula (1)：Wherein, R0For thiophene or derivatives thereof, R1And R2It is identical or different, selected from aromatic rings or derivatives thereof.
- 2. the class of triaryl-ethylene containing thiophene derivant photochromic material according to claim 1, it is characterised in that：R0For Following structure is selected from during thiophene or derivatives thereof：R in its structure4、R5And R6It is identical or different, R4、R5And R6Selected from hydrogen, alkyl, halogen, alkoxy, nitro, carboxyl, ammonia Base, aldehyde radical or cyano group.
- 3. the class of triaryl-ethylene containing thiophene derivant photochromic material according to claim 1, it is characterised in that：R1With R2To be selected from following structure during aromatic rings or derivatives thereof：Wherein R7、R8And R9It is identical or different, R7、R8And R9Selected from hydrogen, alkyl, halogen, alkoxy, nitro, carboxyl, amino, aldehyde Base or cyano group.
- 4. the synthetic method of the class of triaryl-ethylene containing thiophene derivant photochromic material, its feature exist described in claim 1-3 In：(1) one end is contained to aromatic rings, heteroaromatic of formaldehyde substituent or derivatives thereof synthesis is reacted by Corey-Funchs Its dibromo substituent；It is anti-by Suzuki with the aromatic compound containing boric acid or pinacol boric acid ester group or heterocyclic compound again Target product should be obtained；Or (2) by benzophenone derivative and aromatic compound or heterocyclic compound containing p diethylaminobenzoic acid ester group Thing reaction obtains target product by witig reaction.
- 5. the synthetic method of the class of triaryl-ethylene containing thiophene derivant photochromic material according to claim 4, it is special Sign is：The synthetic method (1), including following sequential steps：1. it is miscellaneous to provide the aromatic rings for containing formaldehyde substituent in one end, virtue Ring or derivatives thereof, in dichloromethane solution, under triphenylphosphine and carbon tetrabromide effect, normal-temperature reaction obtains its dibromo and taken For thing；2. the dibromo substituent of gained and the aromatic compound containing boric acid or pinacol boric acid ester group or heterocyclic compound are existed In tetrahydrofuran solution, under potassium carbonate effect, it is catalyzed to obtain target product by tetra-triphenylphosphine palladium.
- 6. the synthetic method of the class of triaryl-ethylene containing thiophene derivant photochromic material according to claim 4, it is special Sign is：The synthetic method (2), including following sequential steps：Benzophenone derivative is provided and contains p diethylaminobenzoic acid ester group Aromatic compound or heterocyclic compound obtain target under potassium tert-butoxide effect in tetrahydrofuran solution by witig reaction Product.
- 7. the class photochromic material of triaryl-ethylene containing thiophene derivant described in claim 1-3 is preparing light control materials, light Application in information recording device, wearable device, chemical-biological detection product, bio-imaging product, anti-fake product.
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| CN108623543A (en) * | 2018-03-21 | 2018-10-09 | 中山大学 | The class photochromic material of triaryl-ethylene containing furan derivatives and its synthetic method and application |
| CN117024401A (en) * | 2023-07-24 | 2023-11-10 | 中国矿业大学 | Triphenylvinyl thiophene compound and preparation method and application thereof |
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