4,4′-联吡啶多钼酸盐的合成、结构与变色性质.pdf

物理化学学报( Wuli Huaxue X
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Acta Phys.-Chim.Sin.,2010,26(5):1264-1270
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Article
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4,4'-联呲啶多钼酸盐的合成、结构与変色性质
孙徳慧·张吉林2任慧娟1崔振峰孙德新3
(长春工程学院,长春130012;2中国科学院长春应用化学研究所,稀土资源利用国家重点实验室,长春130022
3装甲兵技术学院,长春130117
摘要:通过水热合成法,合成了4,4“-联吡啶多钼酸喆盐(4,4'- -bipyridine)Mo,Oa?HO)单晶超分子化合物.通过元
素分析、热重一差热分析(TG-DTA)、粉末X射线衍射(XRD)、单品ⅹ射线衍射傅里叶变换红外( FTIR)光谱、紫外-
可见漫反射光谱(UV- VIS DRS)和电子白旋共振(ESR)技术对其组成、热稳定性、结构、光谱和电子特性进行了表
征实验结果表明:该超分子化合物的分子式为CHMo-NOw,在空气中320℃以下不分解.属于单斜晶系(空
间群为P2m),晶胞参数为a=1,22561(19)nm,b=0.552(9)nm,c=1,8385(3)nm,B=103.221(2),V=1,2113(3)nm,
Z2和D.=3,289g·cm3.基于严的最终统计:GOF-40.982,R=0.0228和vR2=0.0557(>2o(の该单晶超分子化合
物由质子化的4,4-联吡啶阳离子和多金属钳酸盐阴离子MoO22及结晶水组成.它们通过氢键、静电引力和分
子间作用力结合在一起的,并构成二维网络结构.样品在光照或加热条件下貝有光致变色和热致变色性质.XRD
和FIR证明,变色前后,样品的结构除轻微的畸变外几乎没有变化;而ESR结果表明,光致变色与热致变色的
机理可能存在差别.该光致和热致变色的超分子化合物能够为变色机理研究提供参考模型,并在传感器和光敏
材料等领域具有潜在应用.
关键词:超分子化合物;多金属氧酸謐;光致变色;热致变色;联吡啶
中图分类号:O641
Synthesis, Structure and Chromic Properties of 4, 4"-bipyridine
Polyoxomolybdate
SUN De-hui" ZHANG Ji-lin REN Hui-juan CUI Zhen-feng SUN De-xin
(Changchun Institute of Technology, Changchun 130012, P. R. China; State Key Laboratory of Rare Earth Resource Utilization,
Changchun institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P.R.China;
The Amour Technology Institute of PLA, Changchun 130117, P. R. China
Abstract: We synthesized a 4, 4 -bipyridine polyoxomolybdate((4, M -bipyridine)Mo/ O )single crystal
supramolecular compound by a hydrothermal method and characterized its composition, thermostability, structure
spectra and electron properties by elemental analysis, thermal avmetric and differential thermal analysis(TG-DTA)
powder X-ray diffraction(XRD), single ystal X-ray diffraction, Fourier transform infrared(TR)spectroscopy, v
Vis diffuse reflectance spectroscopy(uv-vis DRS), and electron spin resonance(ESR). Experimental results show that
the molecular formula of the supramolecular compound is CH u M Mo N O and it does not decompose below 320 C in
air. It belongs to the monoclinic system(space group P/ )with a=1. 22561(19)nm, b=0.55222(9)nm, c=1. 885(3)nm
B-103.221(2) V=1.2113(3)nm, Z=2 and D.=3. 289 g cm. The final statistics based on Fare GOP=0.982, Ri=
0.0228 and WR =0.0557 for >20(). The single crystal supramolecular compound consists of protonated 4, 4
bipyridine cations and polyoxomolybdate [Mo O2]anions as well as lattice water. They form a two dimensiona (2D,
network through hydrogen bonds, electrostatic attraction, and intermolecular forces, The samples show photochromism
Received December 21, 2009; Revised: February 2, 2010;, Published on Web: March 26, 2010.
CorrespondingauthorEmail:dhsun998@gmail.com;Tel:+86-431-85711658
ported by the National Natural Science Foundation of China(087 1083)and Department of Education of Jilin Province.
China(2008-371,2008-210)
国家自然科学基金(20871083)和吉林省教育厂(2008-371,2008-21の资助项目
C Editorial office of Acta Physico-chimica Sinica