Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes cedex, France.
Inorg Chem. 2013 Jan 18;52(2):555-7. doi: 10.1021/ic302477p. Epub 2013 Jan 8.
For the very first time, sulfonium polyoxometalate (POM) assemblies are shown to develop efficient solid-state photochromism in ambient conditions. The optical properties of the already known Rb(0.75)(NH(4))(5.25)[(Mo(3)O(8))(2)O(O(3)PC(CH(2)S(CH(3))(2))OPO(3))(2)]·8H(2)O (1) and a new material (Me(3)S)(4)[Mo(8)O(26)] (2) under UV excitation are investigated by diffuse reflectance spectroscopy, revealing that the color change effect is highly tunable playing with the nature of the POM. A mechanism involving the photoreduction of Mo(6+) cations associated with electron transfers from the sulfonium cations toward the POMs is proposed.
首次发现，在环境条件下，鏻多金属氧酸盐（POM）组装体可高效地表现出固态光致变色性。通过漫反射光谱法研究了已经知晓的 Rb(0.75)(NH(4))(5.25)[(Mo(3)O(8))(2)O(O(3)PC(CH(2)S(CH(3))(2))OPO(3))(2)]·8H(2)O（1）和新材料 (Me(3)S)(4)[Mo(8)O(26)]（2）在紫外光激发下的光学性质，结果表明，通过改变 POM 的性质，可以高度调控变色效果。提出了一种涉及 Mo(6+)阳离子光还原以及鏻阳离子向 POMs 转移电子的机制。
