CN108997390A - A kind of ability of reverse photochromism and fluorescent switch bifunctional material and preparation method thereof - Google Patents
A kind of ability of reverse photochromism and fluorescent switch bifunctional material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000002441 reversible effect Effects 0.000 title claims abstract description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- QTYYZHVEEXVJBW-UHFFFAOYSA-N OC(C1=CC(CC2=NC=CC(C3=CC=NC=C3)=C2)=CC(C(O)=O)=C1)=O.Cl Chemical compound OC(C1=CC(CC2=NC=CC(C3=CC=NC=C3)=C2)=CC(C(O)=O)=C1)=O.Cl QTYYZHVEEXVJBW-UHFFFAOYSA-N 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000013049 sediment Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- -1 unsaturated carbonate hydrogen Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 7
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- BBNQQADTFFCFGB-UHFFFAOYSA-N purpurin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC(O)=C3C(=O)C2=C1 BBNQQADTFFCFGB-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Classifications
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- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
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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
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of ability of reverse photochromism and fluorescent switch bifunctional material, chemical formula is [Eu2(L)(NO3)4(HOCH2CH2OH)2]n, preparation method is as follows: ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Synthesis, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation.Synthetic method of the present invention is simple, raw material is easy to get, is at low cost, is easy to operate, yield is high and favorable reproducibility, and lighting color from it is light yellow become navy blue when, bifunctional material crystal shape and structure can not only be kept not to be changed, and the appearance of fluorescence ON/OFF process is accompanied by colourshifting process, this reversible fluorescence ON/OFF behavior and photochromic properties, after repeatedly circulation, intensity has broad application prospect there is no significantly changing.
Description
Technical field
The invention belongs to functional complexes technical field of chemistry, and in particular to a kind of ability of reverse photochromism and fluorescent switch are double
Functional material and preparation method thereof.
Background technique
Metal organic frame (Metal-Organic Frameworks, MOFs) is one kind by organic ligand and metal ion
Or the hybrid inorganic-organic materials with molecule internal pore that cluster is self-assembly of by coordinate bond.It is organic in MOFs
The arrangement of ligand and metal ion has apparent directionality, is capable of forming the frame gap structure of high-sequential, makes its performance
Different optical property out, so that determining it in daily life has unusual significance.For example, photoinduced electron
Migration coordination polymer has very huge potential using value in terms of the development and utilization of solar energy.Such compound
Building is one of Research approach in recent years, introduces metal using organic photochromic group and its derivative as organic ligand
In organic coordination polymer, futuramic light-sensitive material is found by the method for improving material property with high efficiency charge point
The conversion ratio of solar energy is improved from the compound that can replace current expensive solar cell material of ability with great
Meaning.
Purpurine has good photochromic property, very strong electron acceptability and the separation of good intermolecular charge
Ability causes molecular surface that strong polarization and electric-force gradient can occur.Therefore, if be included in as module is constructed
Into polymer frame, it will design synthesis obtains many physical properties and the more excellent solid-state material of chemical property.For example:
2011 Nian Zhangjie professor seminar for the first time by lanthanide ion be introduced into photosensitive purpurine system (1,10- bis- (4- carboxyl benzene) -4,
4 '-bipyridyl dichloro salt dissolvings) obtain unique the compound { [Eu (BA) that fluorescent switch property is adjusted with light of an example
(Bpybc)1.5(H2O)]·2NO3·5H2O}n.This compound has shown excellent light and has adjusted fluorescent switch property and non-broken
Bad property read out function, has potential application it in terms of optical storage device and molecular switch.The compound exists
Become blackish green from light yellow under continuous ultraviolet light irradiation, simultaneous fluorescent quenching.This phenomenon is due to fluorescence centre
Transmitting band can be good at being overlapped with the absorption band of photochromic unit, this coincidence will will lead to intermolecular generation energy turn
It moves (RET), leads to fluorescent quenching from the fluorescent emission central transference of excitation to purpurine free radical.Sample after discoloration is in dark
2h, color can take off in air for middle exposure, and fluorescence intensity can be restored to initial state.
The performance of complex depends on its structure, therefore achievees the purpose that control cooperation physical performance by the regulation to structure
It is chemist one of goal to fight for for a long time.It is well known that organic fragrance polyacid compound is a kind of fine
Excellent ligand, by its carboxyl coordination mode diversity and its own have skew structure feature, make it not only
Being good at building has singular structure complex, and is easily formed higher-dimension and the coordination polymer with empty structure feature.?
In this kind of ligand, 5- benzyl bromine M-phthalic acid segment is a kind of structure fragment for being favored of people the most, and what is thus derived matches
Position type of polymer is various, performance is totally different, deep to be liked by numerous workers.Therefore, with 5- benzyl bromine dimethyl isophthalate
With 4,4 '-bipyridyls are raw material, purpurine functionalization flexibility organic ligand are prepared using the method for fabricated in situ, to be had
The metal framework compound of excellent ability of reverse photochromism performance will be a kind of very reasonable thinking.
Summary of the invention
The purpose of the present invention is intended to overcome the shortcomings of existing methods place, provides a kind of ability of reverse photochromism and fluorescence is opened
Close bifunctional material and preparation method.
The first purpose of the invention is to provide a kind of ability of reverse photochromism and fluorescent switch bifunctional material, double function
The chemical formula of energy material is [Eu2(L)(NO3)4(HOCH2CH2OH)2]n, wherein the chemical formula of the L is C26H18N2O8, structure
Formula is as follows:
A second object of the present invention is to provide the preparation sides of a kind of ability of reverse photochromism and fluorescent switch bifunctional material
Method, specifically includes the following steps:
Step 1, ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Preparation
4,4 '-bipyridyls and 5- benzyl bromine dimethyl isophthalate are dissolved in acetonitrile solution A, then at 100 DEG C
22-24h is reacted, is cooled to room temperature after reaction, filters, obtains sediment A；
It is dry after sediment A is washed 3 times with acetonitrile solution B, obtain lurid solid powder；
Lurid solid powder is dissolved in after concentrated hydrochloric acid the hydrolysis 7-12h at 100 DEG C, after hydrolysis
It is cooled to room temperature, filters, obtain sediment B；
It is dry after sediment B is washed with distilled water 3 times, white solid powder is obtained, the white solid powder is
H4LCl2；
Wherein, 4,4 '-bipyridyls, 5- benzyl bromine dimethyl isophthalate, the ratio of acetonitrile solution A and concentrated hydrochloric acid are
1mmol:3-4mmol:40-50ml:10-15ml；
Step 2, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation
By Eu (NO3)3·6H2The H prepared in O and step 14LCl2It is added to acetonitrile solution C and ethylene glycol in the mixed solvent,
Ultrasound 5min at room temperature, obtains mixed reaction solution；
Mixed reaction solution is placed in reaction kettle, 4000min is reacted at 90-100 DEG C, after completion of the reaction with 0.05-0.2
DEG C/cooling rate of min is cooled to room temperature, filter, obtain sediment C, after sediment C wash with acetonitrile solution D drying to get
To [the Eu of faint yellow bulk crystals2(L)(NO3)4(HOCH2CH2OH)2]n；
Wherein, Eu (NO3)3·6H2O、H4LCl2And the ratio of mixed solvent is 1-1.5mmol:0.015mmol:2.6-
5.5ml；
The volume ratio of the acetonitrile solution C and ethylene glycol in the mixed solvent acetonitrile solution C and ethylene glycol is 2.6-3.3:1.
Preferably, the 5- benzyl bromine dimethyl isophthalate the preparation method is as follows:
Step 1, oreinol dioctyl phthalate is dissolved in anhydrous methanol, and the concentrated sulfuric acid is added, flow back 10h at 80 DEG C,
It then cools to room temperature, reaction solution is concentrated, obtain enriched product；Enriched product is dissolved in water, is then extracted with anhydrous ether
It takes, then is washed with saturated sodium bicarbonate to neutrality, is dried overnight with anhydrous sodium sulfate, filtered, filtrate is concentrated to dryness, and obtains 5- first
Base dimethyl isophthalate；
Wherein, the oreinol dioctyl phthalate, anhydrous methanol, the concentrated sulfuric acid ratio be 1mmol:25ml:1ml；
Step 2, oreinol dicarboxylic acid dimethyl ester, N- bromo-succinimide are added in carbon tetrachloride solution,
Then it is charged with azodiisobutyronitrile again, is heated to reflux 36 ± 2h, is cooled to room temperature after completion of the reaction, then uses saturated carbon
Sour hydrogen sodium and saturated sodium-chloride water solution extract respectively, separate and merge organic phase, and through drying, vacuum distillation obtains solid；Institute
It obtains ethyl acetate and n-hexane mixed solvent that solid is 1:10 with volume ratio to recrystallize, obtains 5- benzyl bromine M-phthalic acid diformazan
Ester；
Wherein, oreinol dicarboxylic acid dimethyl ester, N- bromo-succinimide, carbon tetrachloride and azodiisobutyronitrile
Ratio be 0.014mol:0.015mol:100mL:0.0014mol.
Preferably, the sediment A is washed with the acetonitrile solution B of 10ml every time, and the sediment B uses 10-15mL every time
Distillation water washing, the sediment C washs with the acetonitrile solution D of 3mL every time.
Preferably, the concentration of the concentrated hydrochloric acid is 12mol/L.
Compared with the conventional method, the beneficial effects of the present invention are:
The ability of reverse photochromism and fluorescent switch bifunctional material that the present invention prepares are in sunlight or the photograph of 300W xenon lamp
It penetrates down, the color of sample becomes navy blue from faint yellow, which is reversible completely, and the sample of coloring is placed on dark place
1 day or at 120 DEG C heat 20min can slough color.And in the present invention bifunctional material color change along with
The appearance of fluorescence ON/OFF process, fluorescence intensity gradually weaken with light application time increase, this reversible fluorescence ON/OFF behavior
After repeatedly circulation, there is no significantly changing for fluorescence intensity.
Synthetic method of the present invention is simple, raw material is easy to get, is at low cost, is easy to operate, yield is high and favorable reproducibility, and in light
According to color from it is light yellow become navy blue when, be able to maintain crystal shape and structure be not changed, have broad application prospect.
Detailed description of the invention
Fig. 1 is the coordination context diagram for the bifunctional material that embodiment 1 is prepared；
Fig. 2 is the two-dimensional layer structure chart for the bifunctional material that embodiment 1 is prepared；
Fig. 3 is the Magnetic Properties of Three-Dimensional Supramolecular Complex structure chart for the bifunctional material that embodiment 1 is prepared；
Fig. 4 is the thermogravimetric analysis figure for the bifunctional material that embodiment 1 is prepared；
Fig. 5 is the solid uv drs figure that the bifunctional material that embodiment 1 is prepared changes with light application time, interior illustration
For effect picture before and after light color；
Fig. 6 is the ESR spectrogram that the bifunctional material that embodiment 1 is prepared changes with light application time；
Fig. 7 is the PXRD map for the bifunctional material that embodiment 1 is prepared；
Fig. 8 is the infrared spectrogram for the bifunctional material that embodiment 1 is prepared；
Fig. 9 is the solid UV-vis DRS map of ligand used in embodiment 1；
Figure 10 is the bifunctional material electron-donating group and receive the distance between electron group that embodiment 1 is prepared
Figure；
Figure 11 is the exciting light spectrogram for the bifunctional material that embodiment 1 is prepared；
Figure 12 is the fluorescence spectra that the bifunctional material that embodiment 1 is prepared changes with light application time；
Figure 13 is that embodiment 1 bifunctional material prepared fluorescence intensity in ultraviolet light and heat treatment process changes
Become figure；
Figure 14 is the bifunctional material fluorogram and solid uv drs figure that embodiment 1 is prepared.
Specific embodiment
Methods of this invention will be better understood in order to enable art processes personnel, and scheme is practiced, below with reference to specific
The invention will be further described for embodiment and attached drawing, but illustrated embodiment is not as a limitation of the invention.
Experimental method and detection method described in following each embodiments are unless otherwise specified conventional method；The examination
Agent and material can be commercially available on the market unless otherwise specified.
Embodiment 1
A kind of ability of reverse photochromism and fluorescent switch bifunctional material, chemical formula are [Eu2(L)(NO3)4
(HOCH2CH2OH)2]n, wherein the chemical formula of the L is C26H18N2O8, structural formula is as follows:
It is specific the preparation method is as follows:
Step 1,10mmol oreinol dioctyl phthalate is dissolved in 250ml anhydrous methanol, and the 10ml concentrated sulfuric acid is added,
Flow back 10h at 80 DEG C, then cools to room temperature, reaction solution is concentrated, obtain enriched product；Enriched product is dissolved in water,
Then it is extracted with anhydrous ether, then is washed with saturated sodium bicarbonate to neutrality, is dried overnight with anhydrous sodium sulfate, filtered, filtrate
It is concentrated to dryness to get oreinol dicarboxylic acid dimethyl ester, yield 60% is arrived；
Weigh the oreinol dicarboxylic acid dimethyl ester of 4.02g (0.014mol), 2.67g (0.015mol) N- bromo fourth two
Acid imide, being added to and filling the molten amount of 100mL carbon tetrachloride solution is then to weigh 22.3mg in the there-necked flask of 250mL
(0.0014mol) azodiisobutyronitrile is added in above-mentioned reaction vessel, is heated to reflux 36 ± 2h, is cooled to room after completion of the reaction
Then temperature is extracted respectively with saturated sodium bicarbonate and saturated sodium-chloride water solution, separate and merge organic phase, through drying, decompression
Distillation obtains solid；The ethyl acetate and n-hexane mixed solvent that obtained solid is 1:10 with volume ratio recrystallize, and obtain 5- benzyl
Bromine dimethyl isophthalate；
Step 2, ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Preparation
Weigh the 5- benzyl bromine isophthalic two synthesized in the 4,4 '-bipyridyls and 1.72g (3mmol) step 1 of 0.32g (1mmol)
Formic acid dimethyl ester is dissolved in the 100mL single-necked flask containing 40mL acetonitrile solution A, then reacts in 100 DEG C of oil bath
For 24 hours, it is cooled to room temperature after reaction, filters, obtain sediment A；
Sediment A is washed with 10ml acetonitrile solution B every time, is washed altogether 3 times, then the vacuum oven at 40 DEG C is dry
Obtain lurid solid powder；
Light yellow solid powder is dissolved in the 50mL single port bottle containing the concentrated hydrochloric acid that 15mL concentration is 12mol/L, so
12h is reacted in 100 DEG C of oil bath afterwards, is cooled to room temperature after reaction, is filtered, is obtained sediment B, sediment B is used every time
10mL distills water washing, washs 3 times altogether, then the vacuum oven at 60 DEG C is dried to obtain white solid powder 0.5g, yield
About 86.0%；
Step 3, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation
Weigh the H of 9mg (0.015mmol)4LCl2With the Eu (NO of 27mg (1.0mmol)3)3·6H2It is molten that O is dissolved in 2mL acetonitrile
The in the mixed solvent of liquid C and 0.6mL ethylene glycol, ultrasound 5min, obtains mixed reaction solution, mixed reaction solution is shifted at room temperature
It is cold with the cooling rate of 0.05 DEG C/min later in 90 DEG C of isothermal reaction 4000min into the stainless steel autoclave of 25mL
But to room temperature, filtering obtains sediment C, sediment C is washed with 3mL acetonitrile solution D every time, washs 3 times, then dries, i.e., altogether
Obtain [the Eu of faint yellow bulk crystal structure2(L)(NO3)4(HOCH2CH2OH)2]n, yield is 80% (being based on Eu).
Embodiment 2
A kind of ability of reverse photochromism and fluorescent switch bifunctional material, chemical formula are [Eu2(L)(NO3)4
(HOCH2CH2OH)2]n, wherein the chemical formula of the L is C26H18N2O8, structural formula is as follows:
It is specific the preparation method is as follows:
Step 1,10mmol oreinol dioctyl phthalate is dissolved in 250ml anhydrous methanol, and the 10ml concentrated sulfuric acid is added,
Flow back 10h at 80 DEG C, then cools to room temperature, reaction solution is concentrated, obtain enriched product；Enriched product is dissolved in water,
Then it is extracted with anhydrous ether, then is washed with saturated sodium bicarbonate to neutrality, is dried overnight with anhydrous sodium sulfate, filtered, filtrate
It is concentrated to dryness to get oreinol dicarboxylic acid dimethyl ester, yield 60% is arrived；
Weigh the oreinol dicarboxylic acid dimethyl ester of 4.02g (0.014mol), 2.67g (0.015mol) N- bromo fourth two
Acid imide, being added to and filling the molten amount of 100mL carbon tetrachloride solution is then to weigh 22.3mg in the there-necked flask of 250mL
(0.0014mol) azodiisobutyronitrile is added in above-mentioned reaction vessel, is heated to reflux 36 ± 2h, is cooled to room after completion of the reaction
Then temperature is extracted respectively with saturated sodium bicarbonate and saturated sodium-chloride water solution, separate and merge organic phase, through drying, decompression
Distillation obtains solid；The ethyl acetate and n-hexane mixed solvent that obtained solid is 1:10 with volume ratio recrystallize, and obtain 5- benzyl
Bromine dimethyl isophthalate.
Step 2, ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Preparation
Weigh the 5- benzyl bromine isophthalic synthesized in the 4,4 '-bipyridyls and 2.01g (3.5mmol) step 1 of 0.32g (1mmol)
Dicarboxylic acid dimethyl ester is dissolved in the 100mL single-necked flask containing 45mL acetonitrile solution A, then reacts in 100 DEG C of oil bath
22h is cooled to room temperature after reaction, and filtering obtains sediment A；
Sediment A is washed with 10mL acetonitrile solution B every time, is washed altogether 3 times, then the vacuum oven at 40 DEG C is dry
Obtain lurid solid powder；
Light yellow solid powder is dissolved in the 50mL single port bottle containing the concentrated hydrochloric acid that 10mL concentration is 12mol/L, so
10h is reacted in 100 DEG C of oil bath afterwards, is cooled to room temperature after reaction, is filtered, is obtained sediment B, sediment B is used every time
12ml distills water washing, washs 3 times altogether, then the vacuum oven at 60 DEG C is dried to obtain white solid powder 0.55g, yield
About 94.6%；
Step 3, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation
Weigh the H of 9mg (0.015mmol)4LCl2With the Eu (NO of 36mg (1.3mmol)3)3·6H2It is molten that O is dissolved in 3mL acetonitrile
In the mixed solution of liquid C and 1mL ethylene glycol, ultrasound 5min, obtains mixed reaction solution, mixed reaction solution is transferred at room temperature
It is cooling with the cooling rate of 0.1 DEG C/min later in 95 DEG C of isothermal reaction 4000min in the stainless steel autoclave of 25mL
To room temperature, filtering obtains sediment C, sediment C wash with 3mL acetonitrile solution D every time, washs 3 times altogether, then drying to get
To [the Eu of faint yellow bulk crystal structure2(L)(NO3)4(HOCH2CH2OH)2]n, yield is 78% (being based on Eu).
Embodiment 3
A kind of ability of reverse photochromism and fluorescent switch bifunctional material, chemical formula are [Eu2(L)(NO3)4
(HOCH2CH2OH)2]n, wherein the chemical formula of the L is C26H18N2O8, structural formula is as follows:
It is specific the preparation method is as follows:
Step 1,10mmol oreinol dioctyl phthalate is dissolved in 250ml anhydrous methanol, and the 10ml concentrated sulfuric acid is added,
Flow back 10h at 80 DEG C, then cools to room temperature, reaction solution is concentrated, obtain enriched product；Enriched product is dissolved in water,
Then it is extracted with anhydrous ether, then is washed with saturated sodium bicarbonate to neutrality, is dried overnight with anhydrous sodium sulfate, filtered, filtrate
It is concentrated to dryness to get oreinol dicarboxylic acid dimethyl ester, yield 60% is arrived；
Weigh the oreinol dicarboxylic acid dimethyl ester of 4.02g (0.014mol), 2.67g (0.015mol) N- bromo fourth two
Acid imide, being added to and filling the molten amount of 100mL carbon tetrachloride solution is then to weigh 22.3mg in the there-necked flask of 250mL
(0.0014mol) azodiisobutyronitrile is added in above-mentioned reaction vessel, is heated to reflux 36 ± 2h, is cooled to room after completion of the reaction
Then temperature is extracted respectively with saturated sodium bicarbonate and saturated sodium-chloride water solution, separate and merge organic phase, through drying, decompression
Distillation obtains solid；The ethyl acetate and n-hexane mixed solvent that obtained solid is 1:10 with volume ratio recrystallize, and obtain 5- benzyl
Bromine dimethyl isophthalate.
Step 2, ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Preparation
Weigh the 5- benzyl bromine isophthalic two synthesized in the 4,4 '-bipyridyls and 2.29g (4mmol) step 1 of 0.32g (1mmol)
Formic acid dimethyl ester is dissolved in the 100mL single-necked flask containing 50mL acetonitrile solution A, then reacts in 100 DEG C of oil bath
23h is cooled to room temperature after reaction, and filtering obtains sediment A；
Sediment A is washed with 10mL acetonitrile solution B every time, is washed altogether 3 times, then the vacuum oven at 40 DEG C is dry
Obtain lurid solid powder；
Light yellow solid powder is dissolved in the 50mL single port bottle containing the concentrated hydrochloric acid that 10mL concentration is 12mol/L, so
7h is reacted in 100 DEG C of oil bath afterwards, is cooled to room temperature after reaction, is filtered, is obtained sediment B, sediment B is used every time
15ml distills water washing, washs 3 times altogether, then the vacuum oven at 60 DEG C is dried to obtain white solid powder 0.54g, yield
About 92.9%；
Step 3, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation
Weigh the H of 9mg (0.015mmol)4LCl2With the Eu (NO of 40mg (1.5mmol)3)3·6H2It is molten that O is dissolved in 4mL acetonitrile
In the mixed solution of liquid C and 1.5mL ethylene glycol, ultrasound 5min, obtains mixed reaction solution, mixed reaction solution is shifted at room temperature
It is cold with the cooling rate of 0.2 DEG C/min later in 100 DEG C of isothermal reaction 4000min into the stainless steel autoclave of 25mL
But to room temperature, filtering obtains sediment C, sediment C is washed with 3mL acetonitrile solution D every time, washs 3 times, then dries, i.e., altogether
Obtain [the Eu of faint yellow bulk crystal structure2(L)(NO3)4(HOCH2CH2OH)2]n, yield is 75% (being based on Eu).
Since the performance of the embodiment 1-3 bifunctional material prepared is essentially identical, only prepared with embodiment 1
The performance data of bifunctional material illustrates effect of the invention, is specifically shown in Table 1-2 and Fig. 1-14.
The predominant crystal data of 1 embodiment of table, 1 bifunctional material
aR1=∑ | | Fo|-|Fc||/∑|Fo|.bwR2=[∑ w (Fo 2-Fc 2)2/∑w(Fo 2)2]1/2
Main bond distance and bond angle in 2 embodiment of table, 1 bifunctional material
Symmetry operation code: #1:+x, 1+y ,+z；#2:- x, 1-y, 3-z；#3:+x, -1+y ,+z.
It can be seen that [the Eu prepared in the embodiment of the present invention 1 from table 1-22(L)(NO3)4(HOCH2CH2OH)2]nBelong to
Anorthic system, P-1 space group, the coordination environment of Eu such as Fig. 1, crystal structure schematic diagram are shown in 2-3.
It being measured through test, bifunctional material has characteristics that (1) bifunctional material keeps stablizing before 225 DEG C,
The back skeleton collapse of this temperature starts to decompose (Fig. 4)；(2) bifunctional material shows unique photoresponse, in sunlight or
The color of sample becomes navy blue from faint yellow under the irradiation of 300W xenon lamp, which is reversible completely, the sample of coloring
Product, which are placed at dark 1 day or heat 20min at 120 DEG C, can slough color, and this reversible photochromic behavior can
Can be reduced after illumination caused by generating purpurine free radical due to purpurine cation；It diffuses outside its solid violet
Spectrogram newly occurs the characteristic peak of two purpurine free radicals in 404nm and 625nm or so, and with the gradually increasing of light application time
Add, their absorption intensity also gradually increases (Fig. 5-6)；(3) the photochromic process of bifunctional material is not due to photoinduction
Caused by the structural isomerism or photodecomposition of generation, and it is derived from caused by the transfer of intramolecular electronics (Fig. 7-8)；Separately
On the one hand, organic ligand H4LCl2It is not absorbed (Fig. 9) in visible region, and organic ligand is there is no photochromic property, because
The photochromic behavior of this bifunctional material may have relationship with crystal structure, the nitre of carboxyl oxygen (O2) and coordination on ligand
The distance between acid group oxygen (O9, O12) and purpurine nitrogen-atoms (N1) are respectively 3.708,3.465 andMeet power supply
Subbase group and purpurine receive the distance of the electronics transfer between electronic unit (Figure 10)；(4) change of bifunctional material color is adjoint
The appearance of fluorescence ON/OFF process.Fluorescence intensity gradually weakens (Figure 12) with light application time increase, and color sample is from pale yellow
Discoloration is navy blue, and this reversible fluorescence ON/OFF behavior is after repeatedly circulation, and there is no obvious for fluorescence intensity
Change (Figure 13)；Eu3+Characteristic emission peak (Figure 11) and purpurine free radical 625nm or so wide absorption peak can be fine
Ground is overlapped (Figure 14), and energy causes fluorescent quenching from the ligand that the fluorescence centre of excitation is transferred to colored state.
It should be noted that the present invention describes preferred embodiment, but method personnel in the art once know
Basic creative concept, then additional changes and modifications may be made to these embodiments.So appended claims are intended to explain
Being includes preferred embodiment and all change and modification for falling into the scope of the invention.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by the method personnel of this field
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent processes
Within be also intended to include these modifications and variations.
Claims (5)
1. a kind of ability of reverse photochromism and fluorescent switch bifunctional material, which is characterized in that the chemical formula of the bifunctional material
For [Eu2(L)(NO3)4(HOCH2CH2OH)2]n, wherein the chemical formula of the L is C26H18N2O8, structural formula is as follows:
2. the preparation method of ability of reverse photochromism according to claim 1 and fluorescent switch bifunctional material, feature exist
In, specifically includes the following steps:
Step 1, ligand 1,1 '-two (3,5- dicarboxyl benzyl) -4,4 '-bipyridyl chloride H4LCl2Preparation
4,4 '-bipyridyls and 5- benzyl bromine dimethyl isophthalate are dissolved in acetonitrile solution A, are then reacted at 100 DEG C
22-24h is cooled to room temperature after reaction, and filtering obtains sediment A；
It is dry after sediment A is washed 3 times with acetonitrile solution B, obtain lurid solid powder；
After lurid solid powder is dissolved in concentrated hydrochloric acid, the hydrolysis 7-12h at 100 DEG C is cold after hydrolysis
But to room temperature, filtering obtains sediment B；
Sediment B is washed with distilled water 3 times, it is dry, white solid powder is obtained, the white solid powder is H4LCl2；
Wherein, 4,4 '-bipyridyls, 5- benzyl bromine dimethyl isophthalate, the ratio of acetonitrile solution A and concentrated hydrochloric acid are 1mmol:
3-4mmol:40-50ml:10-15ml；
Step 2, [Eu2(L)(NO3)4(HOCH2CH2OH)2]nPreparation
By Eu (NO3)3·6H2The H prepared in O and step 14LCl2It is added to acetonitrile solution C and ethylene glycol in the mixed solvent, in room
The lower ultrasound 5min of temperature, obtains mixed reaction solution；
Mixed reaction solution is placed in reaction kettle, 4000min is reacted at 90-100 DEG C, after completion of the reaction with 0.05-0.2 DEG C/
The cooling rate of min is cooled to room temperature, filtering, obtain sediment C, after sediment C wash 3 times with acetonitrile solution D drying to get
To faint yellow bulk crystal structure [Eu2(L)(NO3)4(HOCH2CH2OH)2]n；
Wherein, Eu (NO3)3·6H2O、H4LCl2And the ratio of mixed solvent is 1-1.5mmol:0.015mmol:2.6-
5.5ml；
The volume ratio of the acetonitrile solution C and ethylene glycol in the mixed solvent acetonitrile solution C and ethylene glycol is 2.6-3.3:1.
3. the preparation method of ability of reverse photochromism according to claim 2 and fluorescent switch bifunctional material, feature exist
In, the 5- benzyl bromine dimethyl isophthalate the preparation method is as follows:
Step 1, oreinol dioctyl phthalate is dissolved in anhydrous methanol, and the concentrated sulfuric acid is added, flow back 10h at 80 DEG C, then
It is cooled to room temperature, reaction solution is concentrated, obtain enriched product；Enriched product is dissolved in water, is then extracted with anhydrous ether, then
It is washed with saturated sodium bicarbonate to neutrality, is dried overnight with anhydrous sodium sulfate, filtered, filtrate is concentrated to dryness, and obtains between 5- methyl
Rutgers；
Wherein, the oreinol dioctyl phthalate, anhydrous methanol, the concentrated sulfuric acid ratio be 1mmol:25ml:1ml；
Step 2, oreinol dicarboxylic acid dimethyl ester, N- bromo-succinimide are added in carbon tetrachloride solution, then
It is charged with azodiisobutyronitrile again, is heated to reflux 36 ± 2h, is cooled to room temperature after completion of the reaction, then uses unsaturated carbonate hydrogen
Sodium and saturated sodium-chloride water solution extract respectively, separate and merge organic phase, and through drying, vacuum distillation obtains solid；Gained is solid
The ethyl acetate and n-hexane mixed solvent that body is 1:10 with volume ratio recrystallize, and obtain 5- benzyl bromine dimethyl isophthalate；
Wherein, the ratio of oreinol dicarboxylic acid dimethyl ester, N- bromo-succinimide, carbon tetrachloride and azodiisobutyronitrile
Example is 0.014mol:0.015mol:100mL:0.0014mol.
4. the preparation method of ability of reverse photochromism according to claim 2 and fluorescent switch bifunctional material, feature exist
In, the sediment A is washed with the acetonitrile solution B of 10ml every time, and the sediment B uses the distillation water washing of 10-15mL every time,
The sediment C is washed with the acetonitrile solution D of 3mL every time.
5. the preparation method of ability of reverse photochromism according to claim 2 and fluorescent switch bifunctional material, feature exist
In the concentration of the concentrated hydrochloric acid is 12mol/L.
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