镧系元素钼系双11系列杂多蓝的离析和性质研究

ISOLATION AND STUDIES ON PROPERTIES OF THE HETEROPOLY BLUES WITH LANTHANIDE COMPLEXES OF DOUBLE-11 SERIES CONTAINING MOLYBDENUM

本文首次报道了镧系元素钼系双11系列两电子杂多蓝K_yH_z[Ln(XMo_(11)O_(39)_2]·nH_2O(X=P,Ln=La、Ce、Pr、Nd、Sm、Gd;X=Si,Ln=Ce、Pr、Sm、Tb、Dy;X=Ge、Ln=Dy)的制备和离析方法.并通过元素分析、红外光谱、可见-紫外光谱、极谱、循环伏安、热分析、ESR、^(31)P NMR、XPS对产物进行了表征及性质研究.结果表明:杂多蓝阴离子结构较之还原前发生了轻微畸变,还原电子具有一定的离域性.在溶液中杂多蓝较还原前的杂多酸(盐)具有略强的氧化能力.溶液中杂多蓝的氧化能力Ln-P(2)>Ln-Si(2).热稳定性Ln-P(2)>Ln-Si(2).该系列杂多蓝还具有较好的抗碱解能力.

Preparation and isolation of two-electron heteropoly blues of Lanthanide complexes of double-11 series containing molybdenum K9H2[Ln(XMo11O39)2] ?? nH2O(X = P, Ln = La, Ce, Pr, Nd, Sm, Gd; X = Si, Ln = Ce, Pr, Sm, Tb, Dy; X = Ge, Ln = Dy) were reported in the paper. They were characterized by elemental analyses, infrared and ultraviolet visible spectra, polarography, cyclic voltammetry, thermal analyses, ESR, 31P NMR, XPS and their properties were studied. All results showed the structure of heteropoly anions had no change obviously but there were slight disorder. Reductive electrons delocalized to some extent. The oxidative order in solution was Ln-P(2) > Ln-Si(2).The heteropoly blues have a good anti-base decomposition ability.