混合价化合物的研究(Ⅱ)─—电化学及现场光谱电化学方法研究非质子介质中Dawson结构杂多阴离子[HAs_2Mo_(18)O_(62)]^(n-)的电还原性质  

Studies on Mixed-Valence Compounds(Ⅱ)─Electrochemical and in situ UV-Vis-Near-IR and FTIR Spectroelectrochemical Studies of Mixed-Valence Heteropolyanion [HAs_2Mo_(18)O_(62)]^(n-) in Aprotic Media

作　　者：张淑艳[1] 孙浩然[1] 杨国昱[1] 徐吉庆[1] 

机构地区：[1]吉林大学化学系,长春130023

出　　处：《高等学校化学学报》1997年第5期772-776,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金;吉林省科学技术委员会科技发展计划及中国科学院福建物质结构研究所结构化学国家重点实验室资助

摘　　要：以电化学和现场紫外－可见－近红外及现场FTIR光谱电化学方法对Dawson结构杂多阴离子［HAS2Mo18O62］5－在非质子介质（CH3CN）中的电还原过程进行了研究．结果表明，该杂多阴离子在非质子介质中经历4步单电子还原反应，所产生的杂多蓝阴离子在近红外区出现宽广的价间电荷转移吸收带，而红外区Mo＝O端键及Mo—O—Mo桥键的特征吸收峰在还原后均有不同程度的红移．The mixed-valence heteropolyanion [HAs2Mo18O62]n- (n= 6, 7, 8, 9) were inves tigated by electrochemical and in-situ UV-Vis-Near-IR and FTIR spectroelectrochemical methods in aprotic media. The results indicate that the heteropolyanion [HAs2Mo18062]5- with four step one electron transfer reductions and the mixed-valence heteropolyanions [HAs2Mo18O62]n- (n = 6, 7, 8, 9) were formed after electroreduction. The mixed-valence heteropolyanions have IVCT bands in Near-IR spectral region- The characteristic absorption of Mo = O double bond and the Mo-O bridge bond shift to low wavenumber after electrore duction.

关 键 词：杂多阴离子 电还原 非质子介质 钼 DAWSON结构 

分 类 号：O641.4[理学—物理化学] O614.612[理学—化学]