[(HOCH_2)_3CNH_3]_6[V_(10)O_(28)]的合成、晶体结构及性质研究

Synthesis,Properties and Crystal Structure of [(HOCH_2)_3CNH_3]_6[V_(10)O_(28)]

合成了一种新的有机-无机盐[(HOCH2)3CNH3]6[V10O28],用IR、UV-Vis光谱及循环伏安法对其进行了表征,测定了化合物的晶体结构.该晶体属单斜晶系,P2(1)/n空间群,化学式为C24H72N6O46V10,分子量为1690.28,晶胞参数:a=1.0428(3)nm,b=1.6398(5)nm,c=1.6079(5)nm,α=90°,β=91.094(5)°,γ=90°,V=2.7490(14)nm3,Z=2,残差因子R1=0.0417,wR2=0.0848.该化合物基于[V10O28]6-同多阴离子,通过与[(HOCH2)3CNH3]+之间的离子间相互作用以及氢键相互作用形成了以[(HOCH2)3CNH3]+为桥联的十钒酸根的有机/无机三维阵列结构.化合物溶液的光色性研究表明从有机分子到钒多酸阴离子之间发生电荷转移;电化学性质表明,该化合物在2.0mol/L H2SO4溶液中随着扫速的增加,还原和氧化的峰电位差距增加.

A new inorganic-organic hybrid supramolecular compound [ （ HOCH2 ）3 CNH3 ]6 [ V10 O28 ] has been synthesized and characterized by IR, UV-Vis spectra, cyclic vohammetry and X-ray diffraction. The compound crystallized in a monoclinic space group P2（1）/n with a =1.042 8（3） nm, b = 1.639 8（5） nm, c = 1.607 9（5） nm, α = 90°,β = 91.094（5）°, γ =90°, V=2.749 0（14） nm^3 and Z = 2, the final R1 = 0.041 7, wR2 = 0.084 8. The compound is based on decavanadate cluster [ V10O28]^6-. The hydrogen bonding interactions and ion actions among [（HOCH2 ）3CNH3 ]^＋ and decavanadate clusters extend it into a three-dimensional supramolecular architecture. Photochromism on the solution of [（HOCH2 ）3CNH3 ]6 [V10O28 ] show that the electron transfer takes place from the organic cation to the polyoxovanadate. The electrochemical property of the compound indicates that potential difference of redox peak relates to the scan rate in the H2 SO4 solution of 2.0 mol/L.