CN103146103A - Mononuclear Fe(II) spin crossover complex/polyvinyl alcohol composite film material and preparation method thereof - Google Patents
Mononuclear Fe(II) spin crossover complex/polyvinyl alcohol composite film material and preparation method thereof Download PDFInfo
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- CN103146103A CN103146103A CN2013100918521A CN201310091852A CN103146103A CN 103146103 A CN103146103 A CN 103146103A CN 2013100918521 A CN2013100918521 A CN 2013100918521A CN 201310091852 A CN201310091852 A CN 201310091852A CN 103146103 A CN103146103 A CN 103146103A
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Abstract
The invention discloses a novel crossover complex/polyvinyl alcohol composite film material and a preparation method thereof and in particular relates to a mononuclear Fe(II) spin crossover complex/polyvinyl alcohol composite film material and a preparation method thereof. PVA (Polyvinyl Alcohol), AP-meSAL=2-hydroxy-3-methyl-N ' -((pyridine-2-yl)-ethylidene)benzohydrazide) is obtained by compounding high polymer PVA and N402 spin crossover monocular complex Fe(AP-MeSAL)2. The composite film material has spin transformation characteristic (T1/<2>=326K, T1/2=319), and has 7K heat stagnation loop.
Description
Technical field
The present invention relates to a kind of novel spin crossover/polymer composite film material preparation, particularly a kind of monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material preparation method.
Background technology
The spin crossover phenomenon was found by L. Cambi first as far back as 1931, was in depth studied later in 1970.And until after 1980, the spin crossover phenomenon just is subject to people and more and more pays close attention to, along with the design of a large amount of Spin crossovers is synthetic, people come to realise Spin crossover and have potential application prospect aspect information storage, device displays, photoswitch, thermoswitch, sensor, thereby have caused new research boom.
But the spin crossover material is to exist with crystal and pulverulence mostly, has limited its widespread use in every field.If can be processed into thin-film material, will make the spin crossover material more be tending towards practical application.In recent years, scientists is utilized the whole bag of tricks, successfully obtained to have the thin-film material of spin crossover character, its method mainly comprises: layer-by-layer, sol-gel method, L B film technology, spin-coating method etc., but these method complicated operations, consuming time and be difficult to make the thin-film material of bulk.Therefore, present goal in research concentrates on the simple method of novel spin crossover composite film material of processability excellence.In addition, that present most study is Fe
II-triazole class title complex and Fe
II-M (CN)
4The spin crossover composite film material that ligand polymer is relevant, and for Fe
II-N
4O
2The research of the composite film material of type monokaryon Spin crossover not yet relates to.
Before this, the off-color material of having reported and the matrix material of polymkeric substance have been subjected to people's favor in actual applications, and this has given us very large enlightenment: the spin crossover material is by the new way of theory to the application facet transition.We select different high molecular polymers to become membrane matrix and different Spin crossovers thus, utilize the hydrogel casting technique to synthesize a kind of spin crossover/polymer composite film material, make this material be applied to different fields, greatly widened its possible scope of application.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material with low cost, simple to operate.
The present invention selects the N that has spin crossover character in nearly room temperature
4O
2Type monokaryon Fe (II) title complex and polyvinyl alcohol (PVA) have prepared the spin crossover composite film material.This laminated film has spin crossover character (T
1/2↑=326 K, T
1/2↓=319 K), and with the heat stagnation winding of 7 K.
Preparation method of the present invention comprises the following steps:
With Fe (AP-MeSAL)
2DMF solution and the aqueous solution of PVA, stirring at room, and standing froth breaking cast in the suspension liquid of homogeneous on clean smooth sheet glass, drying at room temperature gets Fe (AP-MeSAL)
2/ PVA laminated film.
Concrete preparation method of the present invention comprises the following steps:
(1) Fe (AP-MeSAL)
2Be dissolved in respectively DMF and distilled water with PVA;
(2) under the stirring, with Fe (AP-MeSAL)
2DMF solution slowly be added in the aqueous solution of PVA, get cyan suspension liquid, stir the standing froth breaking of room temperature;
(3) suspension liquid with the gained homogeneous casts on clean smooth sheet glass, and ambient temperature overnight is dry, gets cyan target spin crossover/polymer composite film material.
Composite film material of the present invention, success with the combining of monokaryon Spin crossover and high molecular polymer, made up the Spin crossover deficiency in actual applications of present powder and crystal state.The PVA that the present invention selects has good solubility, film-forming properties, chemical stability and environmental friendliness, and the introducing of this polymkeric substance does not affect the spinning change nature of spin crossover material.In addition, working method of the present invention is simple, cost is cheap and repeated good.
Description of drawings
Fig. 1 is Fe (AP-MeSAL)
2The XRD spectra of/PVA laminated film.
Fig. 2 is Fe (AP-MeSAL)
2The Raman spectrogram of/PVA laminated film.
Fig. 3 is Fe (AP-MeSAL)
2The scanning electron microscope of/PVA laminated film (SEM) figure (A is planar S EM figure, and B is high power section SEM figure).
Fig. 4 is Fe (AP-MeSAL)
2The alternating temperature susceptibility curve of/PVA laminated film.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to following embodiment.
Embodiment 1: laminated film synthetic
Under strong magnetic agitation, 1.0 g PVA white particles slowly are added in 9 mL distilled water, 2-3 h are stirred in 55 ℃ of water-baths, get the solution of clear.Then with 1 mL Fe (AP-MeSAL)
2The DMF solution of (0.15 g) slowly is added in mentioned solution, gets cyan suspension liquid, continues to stir 3 h, the standing 2-4 h of room temperature is to eliminate the microvesicle in solution, the suspension liquid of gained is cast on clean smooth sheet glass, and ambient temperature overnight is dry, gets blackish green Fe (AP-MeSAL)
2/ PVA laminated film.
Embodiment 2: pure PVA thin film technology
Utilize method same in embodiment 1 to prepare pure PVA film.
[0017]Embodiment 3: the sign of composite film material
(1) XRD spectra of composite film material
The XRD spectra of composite film material adopts Advance D8 type X-powder diffractometer to measure.Found out by Fig. 1: the XRD spectra of pure PVA film only shows a broad peak, shows that polymer P VA exists with amorphous form.And simple compound F 17-hydroxy-corticosterone e (AP-MeSAL)
2Powder presents obvious crystalline state diffraction peak, and degree of crystallinity is higher.As compound F 17-hydroxy-corticosterone e (AP-MeSAL)
2After forming laminated film with polymer P VA, both shown Fe (AP-MeSAL)
2Characteristic diffraction peak, show again the broad peak of PVA, Fe (AP-MeSAL) is described
2Successfully be entrained in polymer P VA film.
(2) Raman spectrogram of composite film material
The Raman spectrogram of composite film material adopts Senterra R200-L Raman spectrometer.As can be seen from Figure 2: Fe (AP-MeSAL)
2/ PVA laminated film Raman spectrum characteristic peak and compound F 17-hydroxy-corticosterone e (AP-MeSAL)
2Characteristic peak be consistent, Fe (AP-MeSAL) is described in laminated film
2Basic structure do not change.
(3) SEM of composite film material figure
The microstructure of composite film material is measured and is adopted Hitachi S-4800 type field emission scanning electron microscope.Fig. 3 A demonstrates Fe (AP-MeSAL)
2Form with spheroidal particle (approximately 270 nm) is evenly distributed in the PVA gel substantially, further proves compound F 17-hydroxy-corticosterone e (AP-MeSAL)
2Successfully be entrained in polymer P VA film; Fig. 3 B demonstrates the internal structure of laminated film section accordion.
(4) the alternating temperature susceptibility curve of composite film material
The alternating temperature susceptibility employing U.S. Quantum Design MPMC SQUID-XL5 magnetic measurement system of composite film material.Found out by Fig. 4, this spin crossover laminated film has spin and changes (T
1/2↑=326 K, T
1/2↓=319 K), and with the heat stagnation winding of 7 K.
Claims (4)
1. a monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material, is characterized in that it is by Spin crossover Fe (AP-MeSAL)
2Obtain (PVA=polyvinyl alcohol with the high molecular polymer polyvinyl alcohol is compound; AP-MeSAL=2-hydroxy-3-methyl-N'-((pyridin-2-yl)-ethylidene) benzohydrazide), this composite film material not only has spinning change nature (T
1/2↑=326 K, T
1/2↓=319 K), and with the heat stagnation winding of 7 K.
2. press the described a kind of monokaryon Fe of claims 1 (II) Spin crossover/polyvinyl alcohol compound film material preparation method, it is characterized in that comprising the following steps: with Fe (AP-MeSAL)
2DMF solution and the aqueous solution of PVA, stirring at room and standing froth breaking, the suspension liquid of homogeneous cast on clean smooth sheet glass, drying at room temperature gets Fe (AP-MeSAL)
2/ PVA laminated film.
3. a monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material preparation method is characterized in that comprising the following steps:
(1) Fe (AP-MeSAL)
2Be dissolved in respectively DMF and deionized water with PVA;
(2) under the stirring, with Fe (AP-MeSAL)
2DMF solution slowly be added in the aqueous solution of PVA, get cyan suspension liquid, stirring at room, the standing froth breaking of room temperature;
(3) the cyan suspension liquid with the homogeneous of gained casts on clean smooth sheet glass, ambient temperature overnight, and drying gets cyan target Fe (AP-MeSAL)
2/ PVA composite film material.
4. the described monokaryon Fe of claim (II) Spin crossover/application of polyvinyl alcohol compound film material in molecule storage, molecular switch and molecule displays part.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018296A (en) * | 2014-06-11 | 2014-09-03 | 新疆大学 | Method for preparing spinning cross composite fiber membrane through high-voltage electrostatic spinning technology |
| CN104091628A (en) * | 2014-06-26 | 2014-10-08 | 中山大学 | Conductive spinning crossover compound material, preparing method of conductive spinning crossover compound material and application of conductive spinning crossover compound material |
| CN106170695A (en) * | 2014-09-25 | 2016-11-30 | Tdk株式会社 | Gas detecting material, gas detecting tape and lithium rechargeable battery |
| CN108558954A (en) * | 2018-05-08 | 2018-09-21 | 东南大学 | A kind of spin crossover-goes up conversion nano compound material and its preparation method and application |
-
2013
- 2013-03-21 CN CN201310091852.1A patent/CN103146103B/en not_active Expired - Fee Related
Non-Patent Citations (5)
| Title |
|---|
| FRANZ RENZ，ET AL: "Anisotropic effect after stretching of the spin-crossover compound [Fe(Ⅱ)(2,6-bis-(benzimidazol-2"-yl)pyridine)2](ClO4)2 in polyvinylalcohol polymer matrix", 《MOL. CRYST. AND LIQ. CRYS.》 * |
| FRANZ RENZ，ET AL: "Anisotropic effect after stretching of the spin-crossover compound [Fe(Ⅱ)(2,6-bis-(benzimidazol-2"-yl)pyridine)2](ClO4)2 in polyvinylalcohol polymer matrix", 《MOL. CRYST. AND LIQ. CRYS.》, vol. 335, 24 September 2006 (2006-09-24), pages 531 - 540 * |
| TOSHIHIKO HOSHI，ET AL: "Conformations and electronic structures of dibenzylideneacetone", 《J. CHEM. SOC. PERKIN. TRANS.Ⅱ》 * |
| 王娟娟 等: "自旋交叉纳米粒子的合成及性质研究", 《中国化学会第28届学术年会第8分会场摘要集》 * |
| 王娟娟 等: "自旋交叉纳米粒子的合成及性质研究", 《中国化学会第28届学术年会第8分会场摘要集》, 13 April 2012 (2012-04-13), pages 87 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018296A (en) * | 2014-06-11 | 2014-09-03 | 新疆大学 | Method for preparing spinning cross composite fiber membrane through high-voltage electrostatic spinning technology |
| CN104091628A (en) * | 2014-06-26 | 2014-10-08 | 中山大学 | Conductive spinning crossover compound material, preparing method of conductive spinning crossover compound material and application of conductive spinning crossover compound material |
| CN106170695A (en) * | 2014-09-25 | 2016-11-30 | Tdk株式会社 | Gas detecting material, gas detecting tape and lithium rechargeable battery |
| CN108558954A (en) * | 2018-05-08 | 2018-09-21 | 东南大学 | A kind of spin crossover-goes up conversion nano compound material and its preparation method and application |
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| CN103146103B (en) | 2016-09-28 |
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