CN109232618A - Organic inorganic hybridization polyacid base Rare Earth Derivatives and preparation method thereof and application as photochromic material - Google Patents
Organic inorganic hybridization polyacid base Rare Earth Derivatives and preparation method thereof and application as photochromic material Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 32
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 29
- 238000009396 hybridization Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 12
- 239000011975 tartaric acid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 230000002441 reversible effect Effects 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 14
- 238000005562 fading Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 9
- 229910052724 xenon Inorganic materials 0.000 abstract description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 239000000523 sample Substances 0.000 description 32
- 238000010586 diagram Methods 0.000 description 16
- 238000002845 discoloration Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- -1 Ion Compound Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FHBZRIUETNRWFT-UHFFFAOYSA-N C[Cl](C)(C)C Chemical compound C[Cl](C)(C)C FHBZRIUETNRWFT-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
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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
-
- 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
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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Abstract
The invention belongs to polyacid base photochromic material preparation technical fields, provide the polyacid base Rare Earth Derivatives of an example organic inorganic hybridization, and molecular formula is [N (CH3)4]6NaH9[Ho(C4H2O6)(α‑PW11O39)]2·27H2O, which is by HoCl3·6H2O, ligand tartaric acid and polyacid presoma K14[P2W19O69(H2O)]·24H2In water, reaction is prepared mixed dissolution O under water bath condition according to a certain percentage.The present invention explores its photochromism processes under the xenon lamp irradiation of 300W, and explores its photochromic rear colour fading process under the conditions of room temperature, 50 ± 5 DEG C and 80 ± 5 DEG C respectively, finds photochromic mechanism mainly by W6+→W5+Caused by electric charge transfer, it can be used as photochromic material, especially ability of reverse photochromism material.
Description
Technical field
The invention belongs to polyacid base photochromic material technical fields, and in particular to an example organic inorganic hybridization polyacid base is dilute
Native derivative and preparation method thereof and application as photochromic material.
Background technique
The covalent material of organic inorganic hybridization has excellent physical and chemical performance, in fields such as catalysis, material science
There are extensive research and application.More metal hydrochlorides, abbreviation polyacid, due to its significant stability, catalysis and magnetic performance,
It was widely studied in recent years.Polyacid multiple tooth is matched as a kind of inorganic with the oxygen-enriched surface of nucleophilic and structure diversity
Body can form complex with metallic ion coordination, and show good magnetics, photochromic and photoelectric properties.Pass through
Covalent linkage effect, organic carboxyl acid ligand is introduced into polyacid and synthesizes organic-inorganic hybrid material, is one very effective
Synthetic strategy, the oxygen atom on carboxylic acid can replace the oxygen atom in polyacid on metal oxygen polyhedron to form covalent bond.
In recent years, the organic inorganic hybridization rare earth polyacid derivative of carboxylic acid connection is gradually reported, most of exhibitions
Reveal the dumbbell shape structure of dimerization.In the system, the omission of polyacid constructing block is embedded by self assembling process rare earth ion
Position, while the polyacid constructing block that organic carboxyl acid ligand replaces as bridging ligand connection lanthanide ion is formed with light-induced variable
The functionalization material of color, fluorescence and magnetic performance.Based on this synthetic strategy, 2009, applicant synthesized a series of 2:2 types
Monosubstituted rare earth polyacid derivative [(α-PW11O39)Ln(H2O)(η2,μ-1,1)CH3COO}2]10− (Ln=Sm3+, Eu3+,
Gd3+, Tb3+, Ho3+And Er3+) (referring to J. Niu, K. Wang, H. Chen, et al.Cryst. Growth. Des.2009, 9, 4362).2012, applicant replaced acetic acid Hgand with oxalate ligand in the synthesis process, and successfully synthesizes
A series of structures similar rare earth polyacid derivatives [(α-PW11O39)Ln(H2O)]2(C2O4)}10− (Ln = Dy3+, Ho3+
And Er3+) (referring to S. Zhang, Y. Wang, J. Zhao, et al.Dalton Trans., 2012, 41,
3764).2015, a series of rare-earth base arsenowolframic acid salt K of double carboxylic acid bridge joints20Li2[Ln3(μ3-OH)(H2O)8(AsW9O33)
(AsW10O35(mal))]2·17H2O (Ln = Dy3+, Tb3+, Gd3+, Eu3+And Sm3+) be reported, wherein containing Dy3+Ion
Compound have slow magnetic relaxation (referring to P. Ma, R. Wan, Y. Si, et al.Dalton Trans. 2015,44, 11514).For the property of polyacid itself, it can receive one or more in the Undec situation of skeleton
Electronics forms the heteropoly blue of mixed valence.In the polyacid sill of organic inorganic hybridization, pass through the ligand of intramolecular to metal
Its photochromic performance may be implemented in electric charge transfer between ion.
Summary of the invention
The purpose of the present invention is to provide an example organic inorganic hybridization polyacid base Rare Earth Derivatives and preparation method thereof and make
For the application of photochromic material.
To achieve the above object, the present invention adopts the following technical scheme:
An example organic inorganic hybridization polyacid base Rare Earth Derivatives, the polyacid base Rare Earth Derivatives molecular formula are [N (CH3)4]6NaH9
[Ho(C4H2O6)(α-PW11O39)]2·27H2O。
The preparation method of above-mentioned organic inorganic hybridization polyacid base Rare Earth Derivatives comprising following steps: by HoCl3·
6H2O, the tartaric acid as ligand and polyacid presoma K14[P2W19O69(H2O)]·24H2O is dissolved in distilled water, adjust pH to
3.0-3.5 stirs 20-30 min at room temperature, 1.5-2 h is then heated under the conditions of 60 ± 5 DEG C, then four are added while hot
Ammonio methacrylate is simultaneously stirred to react 20-30 min, cooling after reaction, filtering, and filtrate, which stands, is precipitated the blocky crystalline substance of pink
Body, as target product organic inorganic hybridization polyacid base Rare Earth Derivatives.
Wherein, polyacid presoma K14[P2W19O69(H2O)]·24H2O can refer to document (C. M. Tourne, G. F.
Tourne. J. Chem. Soc., Dalton Trans.,1988,2411) it prepares.
Specifically, the HoCl3·6H2O, tartaric acid and K14[P2W19O69(H2O)]·24H2The molar ratio of O is 24:8:
15-18。
Application the present invention provides above-mentioned organic inorganic hybridization polyacid base Rare Earth Derivatives as photochromic material.
Above-mentioned organic inorganic hybridization polyacid base Rare Earth Derivatives have the photochromism of Rapid reversible, therefore, the present invention
Additionally provide its application as ability of reverse photochromism material.The present invention it is found through experiment that: photochromic mechanism be mainly it is more
W in sour tungsten cluster6+→W5+Caused by electric charge transfer.Target product of the present invention has the photochromism of good Rapid reversible
Can, the fading rate of photochromic rear sample is affected by the temperature of ambient enviroment.
Organic inorganic hybridization polyacid base Rare Earth Derivatives of the present invention are synthesized using self assembly strategy, by HoCl3·
6H2O, ligand tartaric acid and polyacid presoma K14[P2W19O69(H2O)]·24H2O is dissolved in water according to a certain percentage, ligand
Tartaric acid is as a kind of carboxylic acid energy and Ho3+Coordination occurs for ion, plays protection Ho3+The effect of ion, prevents Ho3+Ion
It hydrolyzes in aqueous solution；Polyacid presoma K14[P2W19O69(H2O)]·24H2O can be decomposed into { PW in aqueous solution9O33Etc. it is more
Kind polyacid segment, these polyacid segments can be assembled into new polyacid constructing block, and and Ho in aqueous solution3+Ion and carboxylic acid are anti-
It answers, by bonding and bridging effect, forms stable polyacid Rare Earth Derivatives.Compared with traditional polyacid base off-color material, this
Invention has the advantage that
1) present invention uses X-ray single crystal diffraction technology, has carried out accurate characterization to the crystal structure of target product and has conciliate
Analysis；
2) present invention using self assembly in aqueous solution synthetic strategy, operating process is simple, safe operation process, energy consumption are low and
Yield is higher；
3) contain Ho in organic inorganic hybridization polyacid base Rare Earth Derivatives of the present invention3+Rare earth ion, Ho3+Rare earth ion have compared with
Good photochromic properties；
4) present invention has probed into influence of the environment temperature to photochromic rear Sample Fade, for the potential of the photochromic material
Using offer experimental basis and theoretical reference；
5) compared to the existing photochromic rate of polyacid base Rare Earth Derivatives, the photochromic rate of target product of the present invention have compared with
Big raising.
Detailed description of the invention
Fig. 1 is the mallet schematic diagram of 1 anion structure of target product.Show Ho3+Ion is embedded into { PW11In constructing block,
Two { HoPW11Constructing block by the connection of two tartaric acid ligands, forms target product；
Fig. 2 is the infrared spectrogram of colour fading sample after sample and discoloration after 1 primary sample of target product, discoloration.Demonstrate target
It is consistent after product 1 is photochromic and after fading with primary sample skeleton；
Fig. 3 is sample XRD diagram after target product 1 simulates XRD diagram, photochromic preceding sample XRD diagram, fades at room temperature, 50
Under the conditions of DEG C fade after sample XRD diagram, under the conditions of 80 DEG C fade after sample XRD diagram.Target product 1 is demonstrated by photic
Structural framework does not change after discoloration is faded；
Fig. 4 be target product 1 at room temperature, photochromic and colour fading procedure chart.Similar infrared spectroscopy demonstrates target product 1
There is photochromic performance at room temperature；
Fig. 5 is target product 1 at 50 DEG C and 80 DEG C, photochromic rear colour fading procedure chart.Demonstrate 1 light-induced variable of target product
The process of Sample Fade is influenced by environment temperature after color；
Fig. 6 is target product 1 under the irradiation of 300W xenon lamp, time-resolved solid diffusing reflection figure.
Specific embodiment
The present invention is described in further detail below by implementation, but this is not a limitation of the present invention, according to the present invention
Basic thought, various modifications may be made and improve, but as long as not departing from basic thought of the invention, in the range of invention
Within.
Embodiment 1:
An example organic inorganic hybridization polyacid base Rare Earth Derivatives, the polyacid base Rare Earth Derivatives molecular formula are [N (CH3)4]6NaH9
[Ho(C4H2O6)(α-PW11O39)]2·27H2O。
The preparation method of above-mentioned organic inorganic hybridization polyacid base Rare Earth Derivatives comprising following steps:
1) by HoCl3∙6H2Before O (0.227 g, 0.600 mmol), ligand tartaric acid (0.244 g, 0.200 mmol), polyacid
Drive body K14[P2W19O69(H2O)]∙24H2O (2.120 g, 0.375 mmol) is dissolved in 40 mL distilled water, stirs 10-20
After min, pH value is adjusted to 3.2 with the NaOH aqueous solution of 2 mol/L, stirs 20-30 min at room temperature；
2) step 1) acquired solution is put into stirring in water bath in 60 DEG C of water-bath and heats 1 h, tetramethyl chlorine is then added while hot
Change ammonium (0.110 g, 1.000 mmol) and stir 20-30 min, after reaction, filtering cooling to solution, filtrate stands
Slowly pink bulk crystals are precipitated after three weeks to get 1 organic inorganic hybridization polyacid base Rare Earth Derivatives of target product in volatilization.
Embodiment 2:
Target product 1 is placed under the xenon lamp of 300W and irradiates 4 min, the color of target product 1 is changed into navy blue by pink；
Then under dark condition, pink is restored to by placing 3 days in the sample after discoloration at room temperature air.
Embodiment 3:
The colour fading of target product 1 after discoloration is affected by environment temperature, and the target product 1 after discoloration is in 50 ± 5 DEG C of conditions
It is placed 2 days in lower and is restored to pink；Target product 1 after discoloration is to be restored to powder in middle placement 1 day under the conditions of 80 ± 5 DEG C
It is red.
The crystal structure for the target product 1 that the present invention is prepared above-mentioned implementation 1 using X-ray single crystal diffraction technology
Be measured and characterize, cell parameter is as follows: rhombic system, space group arePna2 1 , cell parametera =22.145 (2),b =13.0867 (13),c =52.313 (5),V = 15160(3) Å3,Z =4,R 1=0.0815,wR 2 =
0.1897。
Fig. 1 is the mallet schematic diagram of 1 anion structure of target product.As seen from Figure 1: target product 1 is by one two
Poly- [Ho (C4H2O6)(a-PW11O39)]2 16‒Cation matrix, 3 K+Ion, 6 [N (CH3)4]3+Counter cation and 27 lattices
Hydrone composition, while 7 H+Proton, which is directly added into polyanion, carries out charge balance.H+The addition and acid reaction of proton
Environment is consistent (pH value 3.2).Dimerization [Ho (C4H2O6)(a-PW11O39)]2 16‒Ion is regarded as vacant by 2 lists
[α-the PW of Keggin-type11O39]7‒[Ho (the C of fragment and organic inorganic hybridization4H2O6)]22‒Segment is combined into.[Ho
(C4H2O6)]22‒It can be regarded as by two Ho3+Ion passes through O atom chela in carbonyl atom O and hydroxyl by two tartaric acid ligands
Conjunction is formed.Two [α-PW11O39]7‒Fragment is by [P2W19O69(H2O)]14‒Presoma decomposes generation in acid border, passes through
By Ho3+It is inserted into [α-PW11O39]7‒Omission in so that two [α-PW11O39]7‒With [Ho (C4H2O6)]22‒It is interconnected with one another
(see figure 1).
Fig. 2 is the infrared spectrogram of colour fading sample after sample and discoloration after 1 primary sample of target product, discoloration.It can by Fig. 2
To find out: after 1 primary sample of target product, discoloration sample and discoloration after colour fading sample have similar infrared spectroscopy, 700
1100 cm‒1Correspond to { PW in range11In polyacid skeletonν(P–Oa) (1094 and 1048 cm-1),ν(W–Ot) (951
cm-1),ν(W–Ob) (886 and 816 cm-1) andν(W–Oc) (710 cm-1) stretching vibration.In 3036 and 1620 cm-1It inhales at place
Peak is received to correspond in tartaric acid ligandν(C-H) andν(C=O) symmetrical stretching vibration, 1485 cm-1Locate strong absorption peak to belong to
[(CH3)4N]+In cationν(C-N) stretching vibration.Results of IR is consistent with single crystal diffraction parsing result, it was demonstrated that
Contain polyacid skeleton and tartaric acid ligand, and [(CH in target product 13)4N]+Counter cation (see figure 2).
Fig. 3 be target product 1 simulate XRD diagram, photochromic preceding sample XRD diagram, at room temperature fade after sample XRD diagram,
Under the conditions of 50 DEG C fade after sample XRD diagram, under the conditions of 80 DEG C fade after sample XRD diagram.As seen from Figure 3: target
The photochromic preceding sample XRD diagram of product 1, at room temperature fade after sample XRD diagram, under the conditions of 50 DEG C fade after sample XRD diagram,
Sample XRD diagram and simulation XRD are compared with similar peak position after fading under the conditions of 80 DEG C, peak intensity difference may be due to
The peak XRD of target product 1 (see figure 3) caused by preferred orientation difference during collection.
Fig. 4 be target product 1 at room temperature, photochromic and colour fading procedure chart.Fig. 5 is target product 1 at 50 DEG C and 80
Under the conditions of DEG C, photochromic rear colour fading procedure chart.By Figure 4 and 5 it can be seen that target product 1 the ultraviolet xenon lamp of 300 W irradiation
Under, with the increase of irradiation time, sample gradually becomes navy blue from pink, realizes its colourshifting process.After discoloration, sample exists
Under environment in air at room temperature, original pink is reverted to after 72 h；Sample is in the environment of under the conditions of 50 DEG C, after 48 h
Revert to original pink；Sample reverts to original pink in the environment of under the conditions of 80 DEG C after 24 h.Probe into ring
Influence of the border temperature to colour fading process provides theoretical foundation and experiment basis (see figure for the potential application of the photochromic material
4 and 5).
Fig. 6 is target product 1 under the irradiation of 300 W xenon lamps, time-resolved solid diffusing reflection figure.As seen from Figure 6:
In the solid diffusing reflection figure changed with xenon lamp irradiation time, the band (3.53 eV) of target product 1 is higher than xenon lamp irradiation 4
The band (3.36 eV) of sample after min, and a wider absorption peak occur at 665 nm and belong to W5+→W6+Valence
Between electric charge transfer, it was demonstrated that photochromic (see figure 6) can occur for target product 1.
Claims (5)
1. an example organic inorganic hybridization polyacid base Rare Earth Derivatives, which is characterized in that the polyacid base Rare Earth Derivatives molecular formula is
[N(CH3)4]6NaH9[Ho(C4H2O6)(α-PW11O39)]2·27H2O。
2. the preparation method of organic inorganic hybridization polyacid base Rare Earth Derivatives described in claim 1, which is characterized in that including following
Step: by HoCl3·6H2O, tartaric acid and K14[P2W19O69(H2O)]·24H2O is dissolved in distilled water, adjusts pH to 3.0-3.5,
20-30 min are stirred at room temperature, 1.5-2 h are then heated under the conditions of 60 ± 5 DEG C, then tetramethyl ammonium chloride is added while hot
And 20-30 min are stirred to react, cooling after reaction, filtering, filtrate, which stands, is precipitated pink bulk crystals, as organic
Inorganic hybridization polyacid base Rare Earth Derivatives.
3. the preparation method of organic inorganic hybridization polyacid base Rare Earth Derivatives according to claim 2, which is characterized in that described
HoCl3·6H2O, tartaric acid and K14[P2W19O69(H2O)]·24H2The molar ratio of O is 24:8:15-18.
4. application of the organic inorganic hybridization polyacid base Rare Earth Derivatives as photochromic material described in claim 1.
5. application of the organic inorganic hybridization polyacid base Rare Earth Derivatives as ability of reverse photochromism material described in claim 4.
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| CN102965095A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院福建物质结构研究所 | Inorganic/organic hybrid photochromic material, preparation method and application |
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| CN102965095A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院福建物质结构研究所 | Inorganic/organic hybrid photochromic material, preparation method and application |
Non-Patent Citations (1)
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| PENGTAO MA等: ""Magnetic double-tartaric bridging mono-lanthanide substituted phosphotungstates with photochromic and switchable luminescence properties"", 《J.MATER.CHEM.C》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272439A (en) * | 2019-06-12 | 2019-09-24 | 东北大学 | A kind of synthesis and application of inorganic-organic hybrid oxalic acid gallium fluoride photochromic material |
| CN110272439B (en) * | 2019-06-12 | 2020-10-16 | 东北大学 | Synthesis and application of inorganic-organic hybrid gallium fluoride oxalate photochromic material |
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