CN108690056A - A kind of photochromic material and preparation method thereof with fast response time and wide response range - Google Patents
A kind of photochromic material and preparation method thereof with fast response time and wide response range Download PDFInfo
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- CN108690056A CN108690056A CN201810665602.7A CN201810665602A CN108690056A CN 108690056 A CN108690056 A CN 108690056A CN 201810665602 A CN201810665602 A CN 201810665602A CN 108690056 A CN108690056 A CN 108690056A
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000004044 response Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 33
- -1 phospho Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 21
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- ZARCYQBIHIVLOO-UHFFFAOYSA-N pyridine;triazine Chemical group C1=CC=NC=C1.C1=CN=NN=C1 ZARCYQBIHIVLOO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- CBMYFVSIIYILRH-UHFFFAOYSA-N 2,4,6-tri-4-pyridyl-1,3,5-triazine Chemical compound C1=NC=CC(C=2N=C(N=C(N=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 CBMYFVSIIYILRH-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical class O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention belongs to hybrid inorganic-organic materials synthesis technical fields, more particularly to a kind of hydridization photochromic material and preparation method thereof with fast response time and wide response range, pass through the organic phospho acid of more pyridine units, electron rich to electron deficient and the assembling research in zinc source, prepare the hydridization photochromic material that an example is had excellent performance, the photochromic material is 3D layers of column structure, and wherein organic phospho acid connects Zn2+2D layers are formed, TPT is as column, Zhe Zhong [-ED-EA-ED-EA-]Arrangement mode help to realize it is photochromic, and the compound have wide photoresponse range, the visible color change of bore hole, the charge-separated state of extremely short response time and light irradiation time service life in particular range of wavelengths;Its preparation process is simple, and scientific in principle, raw material is easy to get, at low cost, environmental-friendly, and the photochromic material photoresponse range of preparation is wide, and the response time is short.
Description
Technical field:
The invention belongs to hybrid inorganic-organic materials synthesis technical fields, and in particular to one kind having fast response time
With the hydridization photochromic material of wide response range and preparation method thereof.
Background technology:
It is photochromic that refer to certain compounds molecular structure under the light action of certain wavelength and intensity can change,
So as to cause its corresponding change to absorption peak, that is, color of light, and this change is generally reversible.Photochromic material
Have the characteristics that the reversible switching between two different stable states of two colors, electrons/molecule structure, has been used for ink, makeup
Product, glasses, automobile and other industries, and in molecular switch, ray detection, light limit beam, bio-imaging, bioactivity control, liquid crystal shape
The many aspects such as looks control, molecule machine show wide application prospect.Inorganic-organic hybridization photochromic material is (following
Referred to as hydridization photochromic material) it is one of system of most study.Hydridization photochromic material can not only keep or change
Kind each component feature, and new capability can also be generated according to the synergistic effect between each component.Although hydridization photochromic material
Research has obtained many progress, for example, 201110257499.0 disclose a kind of inorganic/organic hybrid photochromic material and its
Preparation method and application, be related to benzyl viologen bismuth chloride class it is inorganic/synthetic method of organic hybrid photochromic compound with answer
With, benzyl viologen bismuth chloride class it is inorganic/organic hybrid photochromic compound has excellent photochromic properties, ultraviolet and
Under radiation of visible light, discoloration is fast, heats or be placed on darkroom, fades also fast, which can be applicable to optical information storage, protection dress
Decorations, anti-fake and false distinguishing, secrecy, light shutter device, optical information converter, the photochromic sunglasses piece of radiation protection, film sheet
The fields such as material;But the hydridization photochromic material of design and synthesis based on non-photochromic components, especially has quick light efficiency
The hydridization photochromic material answered, it is still extremely challenging.
In many strategies for constructing hydridization photochromic material, to suitable Metal-organic complex (metal-
Organic complexes, MOCs) electron acceptor (electron acceptor, EA) and electron donor are introduced in system
(electron donor, ED) is most important, research shows that the MOCs based on two pyridine derivates often has photochromic spy
Sign is such as based on methyl viologen (MV2+) (or MV2+Derivative) metal phosphate frame and metal organic framework (MOFs), and
In view of inorganic PO4 3-(or HPO3 2-) and organic phospho acid (RPO3 2-) similitude and metal phosphonic acid skeleton structure diversity
And abundant host-guest chemistry, it is expected to more pyridine units introducing metal phosphonic acid system to obtain novel hybride photochromic material.
Invention content:
It is an object of the invention to overcome disadvantage of the existing technology, design provide it is a kind of have fast response time and
The photochromic material and preparation method thereof of wide response range, design (ED and EA based on crystal engineering strategy and molecular level
Optimum organization), with photochromic function be oriented to, to the metal-hydroxy group ethylene-diphosphonic acid (1- of electron rich
hydroxyethylidenediphosphonate,[CH3C(OH)(PO3)2], HEDP) system introduce electron deficient pyridine triazine
(2,4,6-tri (4-pyridyl) -1,3,5-triazine, TPT) unit, by more pyridine units, organic phospho acid and gold
The assembling in category source is probed into, and excellent hydridization photochromic material is prepared, and is provided for the design synthesis and application study of such material
With reference to.
To achieve the goals above, the molecular formula of photochromic material of the present invention is [Zn3(H-HEDP)2(TPT)2
(H2O)]·(H2O), molecular weight 1262.92, anorthic system, space group P ī, cell parameter are β=108.800 (8) °, γ=100.832
(7) °,Z=2, wherein HEDP are metal-hydroxy group ethylene-diphosphonic acid, and TPT is pyridine triazine.
Photochromic material of the present invention has 3D layers of column structure, and asymmetric cell is containing there are three Zn2+, two have
Machine phosphonic acid ligand, two TPT units, a water of coordination molecule and a dissociating water molecule, Zn2+Tetrahedral configuration and triangle is presented
Two kinds of coordination modes of bipyramid configuration, Zn (1)2+/Zn(3)2+Coordination mode be [ZnNO3]Tetrahedron, wherein O atom are from organic
Phosphonic acids, N atoms come from TPT;Zn(2)2+With a N atom from TPT and four O originals from water of coordination and organic phospho acid
Son forms trigonal biyramid configuration;TPT has end group coordination and bridging is coordinated two kinds of coordination modes, and two kinds of bridgings are presented in organic phospho acid
Pattern:The first is with η1:η1:η1:η1:η1:η0:η0:μ5Five Zn of pattern bridging2+;Second is with η1:η1:η0:η1:η1:
η0:η0:μ4Four Zn of pattern bridging2+;Organic phospho acid bridging chelates Zn2+It is formed a diameter of20 membered rings
(20-MR);Further connection forms 2D layers to 20 membered ring construction units, end group TPT ligands by with Zn in layer2+Coordination modification 2D
Layer, bridging TPT ligands by with interlayer Zn2+Coordination forms final 3D layer pole structures;Object hydrone passes through hydrogen bond and 3D master
Body frame interacts;In terms of topology angle, Zn (1)2+It is reduced to 4- connecting nodes, Zn (2)2+With Zn (3)2+Simplify
For 3- connecting nodes, TPT is reduced to connection interlayer Zn2+Short-term, entire frame regard as one (3,4)-connection three node nets
Lattice (are expressed as (3-c)3(4-c), corresponding point group symbol are (4122)(4·6·104)(4·6·8)2)。
The detailed process that the present invention prepares the photochromic material is:
(1) 1mmol source metals, 0.6~2.4mmol organic phosphines source, 5mL water and 1.5mmol oxalic acid or 4mmol are fluorinated
Lithium is uniformly mixed and obtains mixture;
(2) mixture made of step (1) is fitted into the stainless steel high-pressure reaction vessel with ptfe autoclave,
The good rodlike clear crystal of crystallinity is obtained within 7 days in 145 DEG C of crystallization;
(3) it by rodlike clear crystal obtained by step (2) successively through deionized water washing, suction filtration, and is dried at room temperature for, i.e.,
Hybrid inorganic-organic photochromic crystal is prepared.
Source metal of the present invention is zinc oxide;Organic phosphine source is 1-hydroxy ethylidene-1,1-diphosphonic acid;The appearance of stainless steel cauldron
Product is 20mL.
Compared with prior art, the present invention passing through the organic phospho acid and zinc of more pyridine units, electron rich to electron deficient
The assembling in source is studied, and the hydridization photochromic material that an example is had excellent performance is prepared, which is 3D layers of column knot
Structure, wherein organic phospho acid connect Zn2+2D layers are formed, TPT is as column, Zhe Zhong [-ED-EA-ED-EA-]Arrangement mode contribute to
Realize it is photochromic, and experiment show the compound have wide photoresponse range (X-ray, ultraviolet light to sunlight), it is naked
The visible color change of eye, the charge of extremely short response time (0.1s) and light irradiation time service life in particular range of wavelengths
Detach state;Its preparation process is simple, and scientific in principle, raw material is easy to get, at low cost, environmental-friendly, the photochromic material light of preparation
Response range is wide, and the response time is short.
Description of the drawings:
Fig. 1 is the structure chart of photochromic material of the present invention, wherein (a) is the mallet figure of 20 membered rings;(b) it is 2D layers
Polyhedron figure;(c) it is 3D column layer structures;(d) it is topological diagram.
Fig. 2 is that photochromic material of the present invention is schemed outside the solid violet of different light application times.
Fig. 3 is electron spin resonance figure of the photochromic material of the present invention in different light application times.
Fig. 4 is light-induced variable chromatic graph of the photochromic material of the present invention under different light sources.
Specific implementation mode:
The invention will be further described by way of example and in conjunction with the accompanying drawings.
The molecular formula of photochromic material described in the present embodiment is [Zn3(H-HEDP)2(TPT)2(H2O)]·(H2O), molecule
Amount is 1262.92, anorthic system, space group Pī, cell parameter is α=105.647 (7) °, β=108.800 (8) °, γ=100.832 (7) °,
Z=2, wherein HEDP are metal-hydroxy group ethylene-diphosphonic acid, and TPT is pyridine triazine.
Photochromic material described in the present embodiment has 3D layers of column structure (as shown in Figure 1), and asymmetric cell contains
Three Zn2+, two organic phosphonic acid ligands, two TPT units, a water of coordination molecule and a dissociating water molecule, Zn2+It presents
Two kinds of coordination modes of tetrahedral configuration and trigonal biyramid configuration, Zn (1)2+/Zn(3)2+Coordination mode be [ZnNO3]Tetrahedron,
Wherein O atom comes from organic phospho acid, and N atoms come from TPT;Zn(2)2+With from TPT a N atom and from water of coordination and
Four O atoms of organic phospho acid form trigonal biyramid configuration;There is TPT end group coordination and bridging to be coordinated two kinds of coordination modes, have
Two kinds of bridging patterns are presented in machine phosphonic acid:The first is with η1:η1:η1:η1:η1:η0:η0:μ5Five Zn of pattern bridging2+;Second
It is with η1:η1:η0:η1:η1:η0:η0:μ4Four Zn of pattern bridging2+;Organic phospho acid bridging chelates Zn2+It is formed a diameter of20 membered rings (20-MR) (Fig. 1 a);Further connection forms 2D layers to 20 membered ring construction units, end group TPT
Ligand by with Zn in layer2+Coordination modification 2D layers (Fig. 1 b), bridging TPT ligands by with interlayer Zn2+Coordination forms final 3D
Layer pole structure (Fig. 1 c);Object hydrone is interacted by hydrogen bond and 3D main body frames;In terms of topology angle, Zn
(1)2+It is reduced to 4- connecting nodes, Zn (2)2+With Zn (3)2+3- connecting nodes are reduced to, TPT is reduced to connection interlayer Zn2+It is short
Line, three node grids that entire frame regards one (3,4)-connection as (are expressed as (3-c)3(4-c), corresponding point group symbol are
(4·122)(4·6·104)(4·6·8)2) (Fig. 1 d).
The detailed process that the present embodiment prepares the photochromic material is:
(1) 1mmol source metals, 0.6~2.4mmol organic phosphines source, 5mL water and 1.5mmol oxalic acid or 4mmol are fluorinated
Lithium is uniformly mixed and obtains mixture;
(2) mixture made of step (1) is fitted into the stainless steel high-pressure reaction vessel with ptfe autoclave,
The good rodlike clear crystal of crystallinity is obtained within 7 days in 145 DEG C of crystallization;
(3) it by rodlike clear crystal obtained by step (2) successively through deionized water washing, suction filtration, and is dried at room temperature for, i.e.,
Hybrid inorganic-organic photochromic crystal is prepared.
Source metal of the present invention is zinc oxide;Organic phosphine source is 1-hydroxy ethylidene-1,1-diphosphonic acid;The appearance of stainless steel cauldron
Product is 20mL.
Embodiment 1:
0.081g zinc oxide, 0.104g lithium fluoride and 0.510g 1-hydroxy ethylidene-1,1-diphosphonic acid monohydrates are added the present embodiment
To 5mL water dissolutions are used in the stainless steel cauldron that 20mL polytetrafluoroethylene (PTFE) is lining, 0.05g TPT are added while stirring, fully
After stirring, the stainless steel cauldron equipped with reaction solution is sealed, crystallization 7 days in 145 DEG C of baking oven, waiting will not after the completion of reacting
The steel reaction kettle that becomes rusty takes out natural cooling at room temperature, the crystal generated in stainless steel cauldron is removed and with deionized water repeatedly
Cleaning 5 times, at room temperature drying obtain no color chips rhabdolith.
The present embodiment carries out single crystal diffraction experiment to being prepared without color chips rhabdolith, and data analysis shows gainedization
Conjunction object is 3D layers of column structure, wherein HEDP chelatings-bridging Zn2+Formed 2D layers, end group TPT ligands by with Zn in layer2+Coordination
Modification 2D layers, bridging TPT ligands by with interlayer Zn2+Coordination forms final 3D layer pole structures, and object hydrone passes through hydrogen bond
It interacts with 3D main body frames.
Embodiment 2:
0.081g zinc oxide, 0.104g lithium fluoride are added to the stainless steel that 20mL polytetrafluoroethylene (PTFE) is lining by the present embodiment
5mL water dissolutions are used in reaction kettle, and 0.55mL 1-hydroxy ethylidene-1,1-diphosphonic acids (60% aqueous solution) and 0.05g are added while stirring
TPT after being sufficiently stirred, the stainless steel cauldron equipped with reaction solution is sealed, crystallization 7 days in 145 DEG C of baking oven wait having reacted
By cooling in such as embodiment 1, washing and dry method after, obtained target product items characterization and result and embodiment
1 is identical.
Embodiment 3:
It is lining that 0.081g zinc oxide, 0.189g oxalic acid dihydrates are added to 20mL polytetrafluoroethylene (PTFE) by the present embodiment
In stainless steel cauldron use 5mL water dissolutions, while stirring be added 0.15mL 1-hydroxy ethylidene-1,1-diphosphonic acids (60% aqueous solution) and
0.05g TPT after being sufficiently stirred, the stainless steel cauldron equipped with reaction solution are sealed, crystallization 7 days, are waited in 145 DEG C of baking oven
By such as cooling in embodiment 1, washing and dry method after the completion of reaction, obtained target product items characterization and result with
Embodiment 1 is identical.
Claims (4)
1. a kind of photochromic material with fast response time and wide response range, it is characterised in that its molecular formula is [Zn3
(H-HEDP)2(TPT)2(H2O)]·(H2O), molecular weight 1262.92, anorthic system, space group P ī, cell parameter areα=105.647 (7) °, β=108.800
(8) °, γ=100.832 (7) °,Z=2, wherein HEDP are metal-hydroxy group ethylene-diphosphonic acid, and TPT is
Pyridine triazine.
2. the photochromic material with fast response time and wide response range according to claim 1, it is characterised in that
The photochromic material has 3D layers of column structure, and asymmetric cell is containing there are three Zn2+, two organic phosphonic acid ligands, two
A TPT units, a water of coordination molecule and a dissociating water molecule, Zn2+Two kinds of tetrahedral configuration and trigonal biyramid configuration is presented
Coordination mode, Zn (1)2+/Zn(3)2+Coordination mode be [ZnNO3]Tetrahedron, wherein O atom come from organic phospho acid, and N atoms come
From TPT;Zn(2)2+It is double that triangle is formed with a N atom from TPT and four O atoms from water of coordination and organic phospho acid
Bore configuration;TPT has end group coordination and bridging is coordinated two kinds of coordination modes, and two kinds of bridging patterns are presented in organic phospho acid:The first
It is with η1:η1:η1:η1:η1:η0:η0:μ5Five Zn of pattern bridging2+;Second is with η1:η1:η0:η1:η1:η0:η0:μ4Pattern
Four Zn of bridging2+;Organic phospho acid bridging chelates Zn2+It is formed a diameter of20 membered rings (20-MR);20 yuan
Further connection forms 2D layers to ring construction unit, end group TPT ligands by with Zn in layer2+2D layers of coordination modification, bridging TPT ligands
By with interlayer Zn2+Coordination forms final 3D layer pole structures;Object hydrone is interacted by hydrogen bond and 3D main body frames;
In terms of topology angle, Zn (1)2+It is reduced to 4- connecting nodes, Zn (2)2+With Zn (3)2+It is reduced to 3- connecting nodes, TPT
It is reduced to connection interlayer Zn2+Short-term, entire frame regard as one (3,4)-connection three node grids (be expressed as (3-c)3
(4-c), corresponding point group symbol are (4122)(4·6·104)(4·6·8)2)。
3. a kind of preparation method of photochromic material as claimed in claim 2, it is characterised in that specifically preparation process is:
(1) 1mmol source metals, 0.6~2.4mmol organic phosphines source, 5mL water and 1.5mmol oxalic acid or 4mmol lithium fluoride are mixed
Conjunction uniformly obtains mixture;
(2) mixture made of step (1) is fitted into the stainless steel high-pressure reaction vessel with ptfe autoclave,
145 DEG C of crystallization obtain the good rodlike clear crystal of crystallinity for 7 days;
(3) it by rodlike clear crystal obtained by step (2) successively through deionized water washing, suction filtration, and is dried at room temperature for, that is, prepares
Obtain hybrid inorganic-organic photochromic crystal.
4. the preparation method of photochromic material according to claim 3, it is characterised in that the source metal is zinc oxide;Have
Machine phosphine source is 1-hydroxy ethylidene-1,1-diphosphonic acid;The volume of stainless steel cauldron is 20mL.
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CN109206445A (en) * | 2018-10-30 | 2019-01-15 | 青岛大学 | A kind of rare earth phosphonate photochromic material and preparation method thereof |
CN111116615A (en) * | 2019-10-18 | 2020-05-08 | 青岛大学 | Metal phosphonate material with room-temperature demagnetization effect and preparation method thereof |
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CN109206445A (en) * | 2018-10-30 | 2019-01-15 | 青岛大学 | A kind of rare earth phosphonate photochromic material and preparation method thereof |
CN109206445B (en) * | 2018-10-30 | 2020-09-11 | 青岛大学 | Rare earth phosphonate photochromic material and preparation method thereof |
CN111116615A (en) * | 2019-10-18 | 2020-05-08 | 青岛大学 | Metal phosphonate material with room-temperature demagnetization effect and preparation method thereof |
CN111116615B (en) * | 2019-10-18 | 2023-08-18 | 青岛大学 | Metal phosphonate material with room temperature demagnetizing effect and preparation method thereof |
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