CN103146103B - Monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material and preparation method - Google Patents
Monokaryon Fe (II) Spin crossover/polyvinyl alcohol compound film material and preparation method Download PDFInfo
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- CN103146103B CN103146103B CN201310091852.1A CN201310091852A CN103146103B CN 103146103 B CN103146103 B CN 103146103B CN 201310091852 A CN201310091852 A CN 201310091852A CN 103146103 B CN103146103 B CN 103146103B
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Abstract
The present invention relates to the preparation of novel spin crossover/polymer composite film material, especially a kind of FeⅡ‑N4O2The preparation method of type monokaryon Fe (II) coordination compound/polyvinyl alcohol compound film material.It is by high molecular polymer PVA and FeⅡ‑N4O2Type spin crossover mononuclear complex Fe (AP MeSAL)2It is combined and obtains, AP MeSAL=2 hydroxyl 3 methyl N ' ((pyridine 2 ethylidene) benzoyl hydrazine.This composite film material has the spinning change nature of adjoint 7K heat stagnation winding, and spinning temperature is respectively T1/2↑=326 K and T1/2↓=319 K。
Description
Technical field
The present invention relates to the preparation of a kind of novel spin crossover/polymer composite film material, particularly a kind of monokaryon Fe
(II) preparation method of Spin crossover/polyvinyl alcohol compound film material.
Background technology
Spin crossover phenomenon was found by L. Cambi first as far back as 1931, was in depth studied after 1970.And
Until after 1980, spin crossover phenomenon is just more and more paid close attention to by people, along with substantial amounts of Spin crossover
Design synthesis, people come to realise Spin crossover in information storage, device displays, photoswitch, thermal switch, biography
There is potential application prospect in the aspects such as sensor, thus has caused new research boom.
But, spin crossover material is to exist with crystal and pulverulence mostly, limits its extensive in every field
Application.If thin-film material can be processed into, spin crossover material will be made to more they tend to actual application.In recent years, scientist
Utilize various method, have successfully been obtained the thin-film material with spin crossover character, its method specifically includes that LBL self-assembly
Technology, sol-gel process, L B film technology, spin-coating method etc., but the operation of these methods is complicated, time-consuming and is difficult to make bulk
Thin-film material.Therefore, current goal in research concentrates on the excellent novel spin crossover composite film material of processability
In simple method.It addition, that current most study is FeⅡ-triazole coordination compound and FeⅡ- M(CN)4Coordination polymerization
The spin crossover composite film material that thing is relevant, and for FeⅡ-N4O2The composite film material of type monokaryon Spin crossover
Research not yet relate to.
Before this, the off-color material reported and the composite of polymer are favored by people the most, this
Give the enlightenment that we are the biggest: spin crossover material by theory to the new way of application aspect transition.Thus we select difference
High molecular polymer film forming matrix and different Spin crossovers, utilize hydrogel casting technique to synthesize a kind of spin
Intersection/polymer composite film material, makes this materials application in different fields, has significantly widened its possible scope of application.
Summary of the invention
It is an object of the invention to provide a kind of with low cost, simple to operate monokaryon Fe (II) spin crossover of preparing to coordinate
The method of thing/polyvinyl alcohol compound film material.
The present invention selects the N in nearly room temperature with spin crossover character4O2Type monokaryon Fe (II) coordination compound and polyvinyl alcohol
(PVA) spin crossover composite film material it is prepared for.This laminated film has spin crossover character (T1/2↑=326 K, T1/2↓=
319 K), and with the heat stagnation winding of 7 K.
The preparation method of the present invention comprises the following steps:
By Fe (AP-MeSAL)2DMF solution and the aqueous solution of PVA, be stirred at room temperature, and stand froth breaking, by homogeneous
Suspension cast on the most smooth glass plate, drying at room temperature, obtain Fe (AP-MeSAL)2/ PVA laminated film.
The concrete preparation method of the present invention comprises the following steps:
(1) Fe(AP-MeSAL)2DMF and distilled water it is dissolved in respectively with PVA；
(2) under stirring, by Fe (AP-MeSAL)2DMF solution be added slowly in the aqueous solution of PVA, obtain cyan
Suspension, stirring, room temperature stands froth breaking；
(3) being cast on the most smooth glass plate by suspension homogeneous for gained, ambient temperature overnight is dried, and obtains blackish green
Target spin crossover/polymer composite film material.
The composite film material of the present invention, successfully being combined in monokaryon Spin crossover and high molecular polymer
Together, compensate for the Spin crossover of current powder and crystal state deficiency in actual applications.The present invention selects
PVA has good dissolubility, film property, chemical stability and environmental friendliness, and, the introducing of this polymer does not affect spin
The spinning change nature of intersection material.It addition, operational approach of the present invention is simple, inexpensive and repeatability good.
Accompanying drawing explanation
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)2(A is plane SEM figure to scanning electron microscope (SEM) figure of/PVA laminated film, and B is high power
Section SEM schemes).
Fig. 4 is Fe (AP-MeSAL)2The variable temperature magnetic susceptibility curve of/PVA laminated film.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following embodiment.
Embodiment 1: the synthesis of laminated film
Under strong magnetic agitation, 1.0 g PVA white particles are added slowly in 9 mL distilled water, water-bath 55 DEG C
Stirring 2-3 h, obtains the solution of clear.Then by 1 mL Fe (AP-MeSAL)2The DMF solution of (0.15 g) slowly adds
In above-mentioned solution, obtaining cyan suspension, continuing stirring 3 h, room temperature standing 2-4 h, will to eliminate the microvesicle in solution
The suspension of gained casts on the most smooth glass plate, and ambient temperature overnight is dried, and obtains blackish green Fe (AP-MeSAL)2/ PVA is multiple
Close thin film.
Embodiment 2: the preparation of pure PVA film
Method same in embodiment 1 is utilized to prepare pure PVA film.
Embodiment 3: the sign of composite film material
(1) XRD spectra of composite film material
The XRD spectra of composite film material uses Advance D8 type X-powder diffractometer to measure.Found out by Fig. 1: pure
The XRD spectra of PVA film only shows a broad peak, shows that polymer P VA is presented in amorphous state.And simple compound
Fe(AP-MeSAL)2Powder presents obvious crystalline state diffraction maximum, and degree of crystallinity is higher.As compound Fe (AP-MeSAL)2Be polymerized
After thing PVA forms laminated film, both showed Fe (AP-MeSAL)2Characteristic diffraction peak, show again the broad peak of PVA, explanation
Fe(AP-MeSAL)2Successfully it is entrained in polymer P VA thin film.
(2) Raman spectrogram of composite film material
The Raman spectrogram of composite film material uses 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 Fe (AP-MeSAL)2Characteristic peak be consistent, say
Bright in laminated film, Fe (AP-MeSAL)2Basic structure do not change.
(3) the SEM figure of composite film material
The microstructure of composite film material measures and uses Hitachi S-4800 type field emission scanning electron microscope.Fig. 3 A shows
Go out Fe (AP-MeSAL)2It is distributed generally uniformly in PVA gel with the form of spheroidal particle (about 270 nm), proves further
Compound Fe (AP-MeSAL)2Successfully it is entrained in polymer P VA thin film；Fig. 3 B demonstrates laminated film section accordion
Internal structure.
(4) the variable temperature magnetic susceptibility curve of composite film material
The variable temperature magnetic susceptibility of composite film material uses U.S. Quantum Design MPMC SQUID-XL5 magnetic measurement system
System.Being found out by Fig. 4, this spin crossover laminated film has spin and changes (T1/2↑=326 K, T1/2↓=319 K), and with 7 K
Heat stagnation winding.
Claims (4)
1. monokaryon Fe (II) coordination compound/polyvinyl alcohol compound film material, it is characterised in that it is with spin crossover
Thing Fe (AP-MeSAL)2It is combined with high molecular polymer polyvinyl alcohol and obtains, AP-MeSAL=2-hydroxy-3-methyl-N'-
((pyridine-2-ethylidene) benzoyl hydrazine), this composite film material shows with 7 K heat stagnation winding in heating and cooling process
Spinning change nature, transition temperature is respectively T1/2↑=326 K and T1/2↓=319 K。
2. the preparation method of a kind of monokaryon Fe (II) coordination compound/polyvinyl alcohol compound film material as described in claim 1, its
It is characterised by comprising the following steps: by Fe (AP-MeSAL)2DMF solution and the aqueous solution of PVA, be stirred at room temperature and stand
Froth breaking, homogeneous suspension casts on the most smooth glass plate, and drying at room temperature obtains Fe (AP-MeSAL)2/ PVA THIN COMPOSITE
Film.
3. the preparation method of monokaryon Fe (II) coordination compound/polyvinyl alcohol compound film material, it is characterised in that include following
Step:
(1) Fe(AP-MeSAL)2DMF and deionized water it is dissolved in respectively with PVA；
(2) under stirring, by Fe (AP-MeSAL)2DMF solution be added slowly in the aqueous solution of PVA, obtain cyan suspension,
Being stirred at room temperature, room temperature stands froth breaking；
(3) the homogeneous cyan suspension of gained is cast on the most smooth glass plate, ambient temperature overnight, it is dried,
Cyan target spin crossover Fe (AP-MeSAL)2/ PVA composite film material.
4. monokaryon Fe (II) coordination compound/polyvinyl alcohol compound film material described in claim 1 is at molecular recording, molecular switch
With the application in molecule displays part.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104018296B (en) * | 2014-06-11 | 2016-10-12 | 新疆大学 | High-voltage electrostatic spinning technology prepares spin crossover composite cellulosic membrane |
| 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 |
| US10224576B2 (en) * | 2014-09-25 | 2019-03-05 | Tdk Corporation | Gas detection material, gas detection tape and lithium ion secondary 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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Non-Patent Citations (3)
| Title |
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| 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;Franz Renz，et al;《Mol. Cryst. and Liq. Crys.》;20060924;第335卷;第532页第1-12行，Scheme 1，第539页第9-11行 * |
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