CN114957313B - Siloxane-bridged tetraphenyl ethylene derivatives, process for their preparation and their use - Google Patents
Siloxane-bridged tetraphenyl ethylene derivatives, process for their preparation and their use Download PDFInfo
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- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000008569 process Effects 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000004044 response Effects 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 87
- 238000006243 chemical reaction Methods 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- -1 phenyl tetraphenyl styrene Chemical compound 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 229940125904 compound 1 Drugs 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- JQFZOEUTRRZDCL-UHFFFAOYSA-N 1-phenyl-2-(1,2,2-triphenylethenyl)benzene Chemical class C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C(=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 JQFZOEUTRRZDCL-UHFFFAOYSA-N 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- YVCYOVLYYZRNJC-UHFFFAOYSA-N (2-methoxyphenoxy)boronic acid Chemical compound COC1=CC=CC=C1OB(O)O YVCYOVLYYZRNJC-UHFFFAOYSA-N 0.000 description 4
- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 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
- 239000003054 catalyst Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- IUALPRJAXOAGOF-UHFFFAOYSA-N (2-prop-2-enoxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1OCC=C IUALPRJAXOAGOF-UHFFFAOYSA-N 0.000 description 1
- UEOCICLWNYTZBO-UHFFFAOYSA-N (3-methoxyphenoxy)boronic acid Chemical group COC1=CC=CC(OB(O)O)=C1 UEOCICLWNYTZBO-UHFFFAOYSA-N 0.000 description 1
- SXLHAMYMTUEALX-UHFFFAOYSA-N (4-methoxyphenoxy)boronic acid Chemical group COC1=CC=C(OB(O)O)C=C1 SXLHAMYMTUEALX-UHFFFAOYSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical group BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GJIYNWRLGOMDEX-UHFFFAOYSA-N bis[[chloro(dimethyl)silyl]oxy]-dimethylsilane Chemical compound C[Si](C)(Cl)O[Si](C)(C)O[Si](C)(C)Cl GJIYNWRLGOMDEX-UHFFFAOYSA-N 0.000 description 1
- UHRAUGIQJXURFE-UHFFFAOYSA-N chloro-[[[chloro(dimethyl)silyl]oxy-dimethylsilyl]oxy-dimethylsilyl]oxy-dimethylsilane Chemical compound C[Si](C)(Cl)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)Cl UHRAUGIQJXURFE-UHFFFAOYSA-N 0.000 description 1
- DMEXFOUCEOWRGD-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(Cl)O[Si](C)(C)Cl DMEXFOUCEOWRGD-UHFFFAOYSA-N 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- KNPNGMXRGITFLE-UHFFFAOYSA-N methylperoxy(phenyl)borinic acid Chemical compound COOB(O)C1=CC=CC=C1 KNPNGMXRGITFLE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a siloxane bridged tetraphenyl ethylene derivative, a preparation method and application thereof, and belongs to the field of material science. The siloxane bridged tetraphenyl ethylene derivative has a structure shown as a formula I, a formula II or a formula III. The siloxane bridged tetraphenyl ethylene derivative with the photochromic performance disclosed by the invention can realize the photochromic effect in a solution state and a solid state, has extremely fast photochromic response, obvious color change and excellent reversibility, and can obtain different color changes by adjusting the molecular structure of a monomer. The preparation method has the advantages of simple process, easily available raw materials, high yield and good repeatability.
Description
Technical Field
The invention relates to the field of material science, in particular to a siloxane bridged tetraphenyl ethylene derivative, a preparation method and application thereof.
Background
Photochromic materials are materials which undergo reversible color change under specific wavelength illumination, and the photochromic materials are accompanied with obvious changes of physical and chemical properties such as absorption spectrum, dielectric constant and the like in the photoisomerization process. The color-changing material comprises two major categories of inorganic and organic, and the organic photochromic material has the characteristics of designable and controllable molecular structure, sensitivity to light sources, high response speed and the like. Common organic photochromic materials include spiropyrans, spirooxazines, azobenzene, diarylethenes, schiff bases, and the like. However, organic photochromic materials based on tetraphenyl ethylene photochromic groups have not been reported.
The photochromic organic micromolecular material has simple processing mode, can be doped in a polymer, can be used for preparing a photochromic glass film by large-area film formation in a spin coating mode and the like, or can be directly doped in glass to prepare the photochromic glass, or can be used for preparing photoelectric devices with excellent comprehensive properties.
Heretofore, indene-fused photochromic naphthopyrans, naphthols and photochromic articles have been prepared by covalent grafting or blending in a polymer such as polyurethane, polymethacrylate, polysilane, etc., as disclosed in chinese patent application publication No. CN102532088B, CN1608216 a. The polyurea material with the side chain containing azobenzene and good thermal stability and high chromophore content is prepared for optical information storage elements, such as Chinese patent application publication No. CN 1884429A. The photochromic contact lens is prepared by thermally polymerizing or photopolymerizing a monomer containing spiropyrans and spirooxazines to obtain a polymer, such as the Chinese patent application publication No. CN 1732078A.
The light effect as a stimulus source has the outstanding advantages of non-direct contact, remote control, rapidness and the like, so that the reversible photochromic material has wide application prospect in the fields of intelligent windows and the like. However, most of the traditional reversible photochromic materials generally have the problems of poor thermal stability, low cycle life, low color change speed and the like, and the development of the reversible photochromic materials in the related fields is seriously restricted.
Disclosure of Invention
The invention aims to provide a siloxane bridged tetraphenyl ethylene derivative, a preparation method and application thereof. The siloxane bridged tetraphenyl ethylene derivative with the photochromic performance disclosed by the invention can realize the photochromic effect in a solution state and a solid state, has extremely fast photochromic response, obvious color change and excellent reversibility, and can obtain different color changes by adjusting the molecular structure of a monomer. The preparation method has the advantages of simple process, easily available raw materials, high yield and good repeatability.
In order to achieve the above object, the present invention provides the following technical solutions:
The first aspect of the invention:
a siloxane-bridged tetraphenyl ethylene derivative having one of the structures of formula i, formula ii or formula iii:
Wherein O-R-O represents a siloxane group; x is selected from heterocyclic groups with a planar structure, or groups containing alkenyl or alkynyl or not taking any group; each X is the same or different.
The siloxane-bridged tetraphenyl ethylene derivative may be the following:
as a specific embodiment: r has a structure shown in formula IV before being connected:
wherein each S independently takes H or halogen; each F independently takes methyl, ethyl or benzene ring, and n is an integer of 0-10.
As a specific embodiment: the heterocyclic group is one of pyrrolyl, furyl, thienyl, pyridyl, indolyl, quinolinyl, purinyl, thiazolyl, oxazolyl, imidazolyl and pyrimidinyl.
As a specific embodiment: and X is a single bond.
As a specific embodiment: n is an integer of 2 to 6.
The second aspect of the invention:
The preparation method of the siloxane bridged tetraphenyl ethylene derivative is characterized in that the siloxane bridged tetraphenyl ethylene derivative is prepared by coupling a compound shown in a formula V, a formula VI and a formula VII with siloxane shown in a formula IV;
In the formula V, the formula VI and the formula VII, each M independently takes H or methane radical; each X is independently selected from a heterocyclic group with a planar structure, or a group containing alkenyl or alkynyl or not taking any group;
each S in the formula IV independently takes H or halogen; each F independently takes methyl, ethyl or benzene ring, and n is an integer of 0-10.
As a more specific embodiment, the method for preparing the siloxane-modified tetraphenyl styrene comprises the following steps:
1) In nitrogen or argon atmosphere, the compound 1, 2-tetra (4-bromophenyl) ethylene, methoxy phenyl boric acid containing X, palladium catalyst, inorganic base and organic solvent are injected into a three-hole flask, stirred and reacted for 6-72 hours at 90-150 ℃, after the reactant is reacted completely, extracted, decompressed and removed the solvent, and the product is purified by silica gel column chromatography to obtain the tetramethoxy phenyl tetraphenyl ethylene or the derivative thereof.
2) Dissolving tetramethoxy phenyl tetraphenyl styrene or its derivative in organic solvent in nitrogen or argon atmosphere, adding boron tribromide at-78-0 deg.c, heating the mixture to room temperature, stirring for 6-48 hr until the reaction is completed, adding ice water to quench, extracting, decompressing to eliminate solvent and obtaining the tetrahydroxy phenyl tetraphenyl styrene or its derivative.
And a third step of: dissolving tetrahydroxyphenyl tetraphenyl styrene or its derivative in an organic solvent flask, stirring with a magnet, adding triethylamine and siloxane (formula IV), extracting until the reaction is complete, removing the solvent under reduced pressure, and purifying the product by silica gel column chromatography to obtain siloxane bridge biphenyl tetraphenyl styrene.
Further, in the step 1) of methoxy phenyl boric acid containing X, X is selected from heterocyclic groups with a planar structure, or groups containing alkenyl or alkynyl or not taking any group. The heterocyclic group with a planar structure is one of pyrrole, furan, thiophene, pyridine, indole, quinoline, purine, thiazole, oxazole, imidazole, pyrimidine and other heterocyclic groups.
When X is an alkenyl or alkynyl containing group, the X-containing methoxyphenylboronic acid may be vinylmethoxyphenylboronic acid, alkynylmethoxyphenylboronic acid.
When X does not take any group, the methoxy phenyl boric acid containing X is 2-methoxy phenyl boric acid, 3-methoxy phenyl boric acid or 4-methoxy phenyl boric acid.
As a specific embodiment, in step 1), the palladium catalyst is palladium chloride, tetraphenylphosphine palladium or ditolylphosphine palladium dichloride.
In a specific embodiment, in step 1), the inorganic base is potassium carbonate, sodium carbonate or cesium carbonate.
In a specific embodiment, in step 1), the organic solvent is N, N dimethylformamide.
In a specific embodiment, in step 2), the organic solvent is dry dichloromethane, tetrahydrofuran or ethyl acetate.
In step 3), as a specific embodiment, the organic solvent is anhydrous tetrahydrofuran; strictly drying triethylamine without water; the molar ratio of tetrahydroxyphenyl tetraphenyl styrene or derivative thereof to the siloxane (formula IV) is 1:2.
A third aspect of the invention:
use of the siloxane-bridged tetraphenyl ethylene derivative as a photochromic material.
Further, the siloxane-bridged tetraphenyl ethylene derivative has a color-changing response wavelength of 330nm to 380nm.
The siloxane-bridged tetraphenyl ethylene derivative is in a solid state or a solution. That is, the siloxane-bridged tetraphenyl ethylene derivative material of the present invention can achieve a photochromic effect in a solution state and a solid state.
As a specific embodiment: the siloxane bridged tetraphenyl ethylene derivative is used for manufacturing color-changing glass, a color-changing glass film or an optical information storage device.
The beneficial effects of the invention are as follows:
The siloxane bridged tetraphenyl ethylene derivative provided by the invention can be used as a photochromic material, and the photochromic material has extremely fast optical response, excellent solubility, simple and various preparation processes and mild reaction conditions, so that the photochromic material is suitable for industrial production.
The siloxane-bridged tetraphenyl ethylene derivative materials of the present invention can be rapidly colorless to yellow or blue or red, etc. (within seconds) under uv light stimulation, both in the liquid state and in the solid state. The color is recovered to be colorless from yellow, blue, red or the like under visible light, the color response speed is high, and the color change is various.
The tetraphenyl ethylene derivative material is suitable for preparing photochromic glass, photochromic glass film, optical information storage device material and other fields.
Drawings
FIG. 1 shows the hydrogen spectrum of compound 1 obtained in example 1 of the present invention, the solution being deuterated chloroform.
FIG. 2 is a silicon spectrum of compound 1 obtained in example 1 of the present invention, the solution being deuterated chloroform.
FIG. 3 is a mass spectrum of compound 1 obtained in example 1 of the present invention, wherein the solution is methylene chloride.
FIG. 4 is a hydrogen spectrum of compound 2 obtained in example 2 of the present invention, the solution being deuterated chloroform.
FIG. 5 is a silicon spectrum of compound 2 obtained in example 2 of the present invention, the solution being deuterated chloroform.
FIG. 6 is a mass spectrum of compound 2 obtained in example 2 of the present invention, wherein the solution is methylene chloride.
FIG. 7 shows the hydrogen spectrum of compound 3 obtained in example 3 of the present invention, the solution being deuterated chloroform.
FIG. 8 is a silicon spectrum of compound 3 obtained in example 3 of the present invention, the solution being deuterated chloroform.
FIG. 9 is a mass spectrum of compound 3 obtained in example 3 of the present invention, wherein the solution is methylene chloride.
FIG. 10 is a hydrogen spectrum of compound 4 obtained in example 4 of the present invention, the solution being deuterated chloroform.
FIG. 11 is a silicon spectrum of compound 4 obtained in example 4 of the present invention, the solution being deuterated chloroform.
FIG. 12 is a mass spectrum of compound 4 obtained in example 4 of the present invention, wherein the solution is methylene chloride.
FIG. 13 is a UV spectrum of Compound 1 obtained in example 1 of the present invention, using a 365nm UV lamp, and tetrahydrofuran as the solution.
FIG. 14 is a liquid chart of Compound 1 obtained in example 1 of the present invention, wherein the ultraviolet lamp was 365nm, and the solution was tetrahydrofuran.
FIG. 15 is a solid view of Compound 1 obtained in example 1 of the present invention, using an ultraviolet lamp at 365nm.
Detailed Description
The following examples are given to illustrate the invention in more detail, it being necessary to note that the following examples are not to be construed as limiting the scope of the invention. Some insubstantial modifications and variations of the invention as per the above-described summary are within the scope of the invention as claimed by those skilled in the art.
Example 1a synthetic route for a siloxane-bridged tetraphenyl ethylene derivative compound 1 is shown below:
The method comprises the following specific steps:
The first step: compound 1, 2-tetrakis (4-bromophenyl) ethylene (3.24 g,5 mmol), 2-methoxyphenylboronic acid (4.56 g,30 mmol), pdCl 2 (355.65 mg,1 mmol), cesium carbonate (2.606 g,4 mmol) were injected into a 250mL three-hole flask, and nitrogen was purged 3 times after degassing. Dimethylformamide (80 ml) was injected into the reaction flask with a syringe. The solution was heated under an inert atmosphere at 95 ℃ for 48 hours, during which time petroleum ether was used: the reaction was monitored on a dichloromethane=4:1 spot (rf=0.3), and after the reaction was complete, cooled to room temperature, the solvent was dried by spinning, ethyl acetate (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous sodium sulfate. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give tetramethoxyphenyl tetraphenyl ethylene (yellow-green solid, 2.91g, yield 77.7%).
And a second step of: in N 2, tetramethoxyphenyl tetraphenyl ethylene (1 g,1.32 mmol) was dissolved in dry dichloromethane (80 ml), boron tribromide (0.52 g,0.64ml,6.6 mmol) was added at-78 ℃ and the resulting mixture was warmed to room temperature, stirred for 24h, the reaction was monitored with dichloromethane spot-plate (rf=0.3), and after the reaction was complete, ice water was added to quench, dichloromethane was extracted, the aqueous layer was again extracted with ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure to give tetrahydroxyphenyl tetraphenyl ethylene (pale yellow solid, 0.832g, 90% yield).
And a third step of: tetrahydroxyphenyl tetraphenyl ethylene (0.5 g,0.715 mmol), anhydrous triethylamine 2ml, dry tetrahydrofuran (50 ml) were placed in a 250ml three-neck flask, stirred with a magnet, 1, 7-dichloro octamethyltetrasiloxane (0.503 g,1.43 mmol) was added, and the reaction was continued for approximately ten seconds with petroleum ether: dichloromethane=1:1 dot plate monitored reaction (rf=0.6), and after the reaction was complete, the solvent was dried by spinning, dichloromethane (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous Na 2SO4. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give tetrasiloxane-bridged phenyltetraphenyl ethylene (yellow-white solid, 0.539g,0.429mmol, 60% yield).
Example 2a synthetic route for a siloxane-bridged tetraphenyl ethylene derivative compound 2 is shown below:
The method comprises the following specific steps:
The first step: compound 1, 2-tetrakis (4-bromophenyl) ethylene (3.24 g,5 mmol), 2-methoxyphenylboronic acid (4.56 g, 30 mmol), pdCl 2 (355.65 mg,1 mmol), cesium carbonate (2.606 g,4 mmol) were injected into a 250mL three-hole flask, and nitrogen was purged 3 times after degassing. Dimethylformamide (80 ml) was injected into the reaction flask with a syringe. The solution was heated under an inert atmosphere at 95 ℃ for 48 hours, during which time petroleum ether was used: the reaction was monitored on a dichloromethane=4:1 spot (rf=0.3), and after the reaction was complete, cooled to room temperature, the solvent was dried by spinning, ethyl acetate (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous sodium sulfate. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give tetramethoxyphenyl tetraphenyl ethylene (yellow-green solid, 2.91g, yield 77.7%).
And a second step of: in N 2, tetramethoxyphenyl tetraphenyl ethylene (1 g,1.32 mmol) was dissolved in dry dichloromethane (80 ml), boron tribromide (0.52 g,0.64ml,6.6 mmol) was added at-78 ℃ and the resulting mixture was warmed to room temperature, stirred for 24h, the reaction was monitored with dichloromethane spot-plate (rf=0.3), and after the reaction was complete, ice water was added to quench, dichloromethane was extracted, the aqueous layer was again extracted with ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure to give tetrahydroxyphenyl tetraphenyl ethylene (pale yellow solid, 0.832g, 90% yield).
And a third step of: tetrahydroxyphenyl tetraphenyl ethylene (0.5 g,0.715 mmol), anhydrous triethylamine 2ml, dry tetrahydrofuran (50 ml) were placed in a 250ml three-neck flask, stirred with a magnet, and dimethyldichlorosilane (0.185 g,1.43 mmol) was added over a period of approximately ten seconds, followed by petroleum ether: dichloromethane=1:1 dot plate monitored reaction (rf=0.5), and after the reaction was complete, the solvent was dried by spinning, dichloromethane (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous Na 2SO4. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give a siloxane bridged phenyl tetraphenyl ethylene (yellow green solid, 0.378g, 0.460 mmol, 65% yield).
Example 3a synthetic route for siloxane-bridged tetraphenyl ethylene derivative compound 3 is shown below:
The method comprises the following specific steps:
The first step: compound 1, 2-tetrakis (4-bromophenyl) ethylene (3.24 g,5 mmol), 2-methoxyphenylboronic acid (4.56 g,30 mmol), pdCl 2 (355.65 mg,1 mmol), cesium carbonate (2.606 g,4 mmol) were injected into a 250mL three-hole flask, and nitrogen was purged 3 times after degassing. Dimethylformamide (80 ml) was injected into the reaction flask with a syringe. The solution was heated under an inert atmosphere at 95 ℃ for 48 hours, during which time petroleum ether was used: the reaction was monitored on a dichloromethane=4:1 spot (rf=0.3), and after the reaction was complete, cooled to room temperature, the solvent was dried by spinning, ethyl acetate (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous sodium sulfate. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give tetramethoxyphenyl tetraphenyl ethylene (yellow-green solid, 2.91g, yield 77.7%).
And a second step of: in N 2, tetramethoxyphenyl tetraphenyl ethylene (1 g,1.32 mmol) was dissolved in dry dichloromethane (80 ml), boron tribromide (0.52 g,0.64ml,6.6 mmol) was added at-78 ℃ and the resulting mixture was warmed to room temperature, stirred for 24h, the reaction was monitored with dichloromethane spot-plate (rf=0.3), and after the reaction was complete, ice water was added to quench, dichloromethane was extracted, the aqueous layer was again extracted with ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure to give tetrahydroxyphenyl tetraphenyl ethylene (pale yellow solid, 0.832g, 90% yield).
And a third step of: tetrahydroxyphenyl tetraphenyl ethylene (0.5 g, 0.015 mmol), anhydrous triethylamine 2ml, dry tetrahydrofuran (50 ml) were placed in a 250ml three-neck flask and stirred with a magnet, 1, 3-dichloro-tetramethyl-disiloxane (0.2910 g,1.43 mmol) was added, the course of the reaction was approximately ten seconds, and petroleum ether was used: dichloromethane=1:1 dot plate monitored reaction (rf=0.54), and after the reaction was complete, the solvent was dried by spinning, dichloromethane (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous Na 2SO4. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give disiloxane-bridged biphenyl tetrastyrene (white solid, 0.433g,0.45mmol, 63% yield).
Example 4a synthetic route to a siloxane-bridged tetraphenyl ethylene derivative compound 4 is shown below:
The method comprises the following specific steps:
The first step: compound 1, 2-tetrakis (4-bromophenyl) ethylene (3.24 g,5 mmol), 2-methoxyphenylboronic acid (4.56 g,30 mmol), pdCl 2 (355.65 mg,1 mmol), cesium carbonate (2.606 g,4 mmol) were injected into a 250mL three-hole flask, and nitrogen was purged 3 times after degassing. Dimethylformamide (80 ml) was injected into the reaction flask with a syringe. The solution was heated under an inert atmosphere at 95 ℃ for 48 hours, during which time petroleum ether was used: the reaction was monitored on a dichloromethane=4:1 spot (rf=0.3), and after the reaction was complete, cooled to room temperature, the solvent was dried by spinning, ethyl acetate (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous sodium sulfate. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give tetramethoxyphenyl tetraphenyl ethylene (yellow-green solid, 2.91g, yield 77.7%).
And a second step of: in N 2, tetramethoxyphenyl tetraphenyl ethylene (1 g,1.32 mmol) was dissolved in dry dichloromethane (80 ml), boron tribromide (0.52 g,0.64ml,6.6 mmol) was added at-78 ℃ and the resulting mixture was warmed to room temperature, stirred for 24h, the reaction was monitored with dichloromethane spot-plate (rf=0.3), and after the reaction was complete, ice water was added to quench, dichloromethane was extracted, the aqueous layer was again extracted with ethyl acetate, the organic layers were combined, dried over anhydrous sodium sulfate, filtered and the solvent was removed under reduced pressure to give tetrahydroxyphenyl tetraphenyl ethylene (pale yellow solid, 0.832g, 90% yield).
And a third step of: tetrahydroxyphenyl tetraphenyl ethylene (0.5 g,0.715 mmol), anhydrous triethylamine 2ml, dry tetrahydrofuran (50 ml) were placed in a 250ml three-neck flask, stirred with a magnet, 1, 5-dichloro hexamethyltrisiloxane (0.397 g,1.43 mmol) was added and the reaction was continued for approximately ten seconds with petroleum ether: dichloromethane=1:1 dot plate monitored reaction (rf=0.58), and after the reaction was complete, the solvent was dried by spinning, dichloromethane (100 mL) was added, the solution was washed with saturated sodium chloride solution (3×100 mL) and dried over anhydrous Na 2SO4. The solvent was then removed by evaporation on a rotary evaporator. The product was purified by silica gel column chromatography to give trisiloxane-bridged phenyltetraphenyl-ethylene (white solid, 0.492g,0.443mmol, 62% yield).
Application examples
Application example 1
0.01258G of the product powder of the compound 1 obtained in example 1 was weighed by a balance, dissolved in 1000ml of tetrahydrofuran to prepare a solution having a concentration of 1X 10 - mol/L, 2ml of the prepared solution was then placed in a quartz cuvette of 1cm X1 cm by using a pipette, another 2ml of pure tetrahydrofuran solution was used as a control, and an ultraviolet-visible absorption spectrum was recorded by using a TU-1901 double beam ultraviolet-visible spectrophotometer as shown in FIG. 13, an ultraviolet spectrum measured in a transparent state by a solid line, and an ultraviolet spectrum measured by changing the solution into a dark yellow liquid after irradiation at 365nm in a dotted line and 2 seconds.
Application example 2
0.01258G of the product powder of the compound 1 obtained in example 1 was weighed by a balance, dissolved in 1000ml of tetrahydrofuran to prepare a solution having a concentration of 1X 10 -5 mol/L, 8ml of the prepared solution was placed in a glass bottle, irradiated with an ultraviolet lamp having an irradiation wavelength of 365nm for 2 seconds as shown in FIG. 14, the irradiated solution turned dark yellow, and after removal of ultraviolet light for 5 minutes, the solution was returned to a transparent state.
Application example 3
0.01258G of the product powder was weighed by a balance, dissolved in 100ml of tetrahydrofuran to prepare a 1X 10 -4 mol/L solution, which was doped into the Dow Corning 184 in a mass ratio of 1:10, wherein the A component of the Dow Corning 184: the volume ratio of the component B is 10:1, stirring is carried out for 2 minutes, ultrasound is carried out for 5 minutes, after uniform mixing, curing is carried out for 10 hours at 60 ℃, and transparent solid is obtained; the solid was changed to dark yellow after irradiation with an ultraviolet lamp having an irradiation wavelength of 365nm for 2 seconds as shown in FIG. 15, and the solid was restored to a transparent state after removal of ultraviolet light for two minutes.
Claims (8)
1. A siloxane-bridged tetraphenyl ethylene derivative characterized by: has one of the structures shown in formula I, formula II or formula III:
wherein O-R-O represents a siloxane group; and X is a single bond.
2. The siloxane-bridged tetraphenyl ethylene derivative of claim 1, wherein: r has a structure shown in formula IV before being connected:
wherein each S independently takes H or halogen; each F independently takes methyl, ethyl or benzene ring, and n is an integer of 0-10.
3. The siloxane-bridged tetraphenyl ethylene derivative of claim 2, wherein: n is an integer of 2 to 6.
4. A process for the preparation of a siloxane-bridged tetraphenyl ethylene derivative according to claim 1, wherein: is prepared by coupling a compound shown in a formula V, a formula VI and a formula VII with siloxane shown in a formula IV;
in the formula V, the formula VI and the formula VII, each M independently takes H or methane radical; and X is a single bond.
Each S in the formula IV independently takes H or halogen; each F independently takes methyl, ethyl or benzene ring, and n is an integer of 0-10.
5. Use of the siloxane-bridged tetraphenyl ethylene derivative as defined in claim 1 as a photochromic material.
6. The method according to claim 5, wherein the siloxane-bridged tetraphenyl ethylene derivative has a color-changing response wavelength of 330nm to 380nm.
7. The use according to claim 5, wherein: the siloxane-bridged tetraphenyl ethylene derivative is in a solid state or a solution.
8. The use according to claim 5, wherein: the siloxane bridged tetraphenyl ethylene derivative is used for manufacturing color-changing glass, a color-changing glass film or an optical information storage device.
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