三元杂多酸-甲基紫超分子化合物的合成及光谱研究

在水溶液条件下合成了一系列具有Keggin结构的PWxV12 -x MV(x =2 ,4 ,6 ,8,10 )超分子化合物 (PWxV12 -x为具有不同配比的磷钨矾三元杂多酸 ,MV为甲基紫 ) ,并对其紫外光谱 ,红外光谱和荧光光谱进行了研究。结果表明 ,杂多酸阴离子上的端氧与甲基紫阳离子上的N 间通过配合作用相互连结而形成超分子化合物。超分子化合物中仍保持有杂多阴离子的Keggin结构以及甲基紫的基本结构。且随着V的含量增加 ,杂多阴离子的氧化能力增强 ,阴离子PWxV12 -x和阳离子MV的相互作用增强 ,νas(M =Ot) ,νas(M Ob M )和νas(M Oc M )的FTIR吸收峰分别从 96 6 ,886和 80 4cm-1变化至 95 5 ,875和 786cm-1;紫外吸收峰也从 5 19nm移至 5 0 6nm ;用 5 30nm的光激发的荧光发射峰也从 6 92移至 6 4 4nm ,与PWxV12 -x和MV间配合作用的强弱呈现了很好的对应关系。

Synthesis and Spectroscopic Studies of Supermolecules of PWxV12-x-MV

A series of supermolecules of PW(x)V(12 - x)-MV (PW(x)V(12 - x): polyoxometalates x = 2, 4, 6, 8, 10; MV: methyl violet) with Keggin structure were prepared and their characters were studied by electronic spectra, infrared spectra and fluorescence spectra. As a result, the supermolecules were formed by the cooperating action between polyoxometalates and methyl violet. In the supermolecule, the structures of cation and anion are not destroyed. With the content of V increasing, the oxidation ability of polyoxometalates anion is enhanced, and the interaction of methyl violet cation and polyoxometalates anion is enhanced too. The FTIR absorption peaks of nu(as)(M=O(t)), nu(as)(M-O(b)-M) and nu(as)(M-O(c)-M) move from 966, 886, and 804 cm(-1) to 955, 875 and 786 cm(-1), respectively; the UV-Vis absorption peak moves from 519 to 506 nm; the emission peak excited at 530 nm moves from 692 to 644 nm too. These changes are according with the degree of the interaction of polyoxometalates and methyl violet.