A new arylimido derivative of polyoxometalate (Bu4N)2[Mo6O17(NAr)2] [Ar = 2,6-(CH3)2C6H3]: Synthesis, structure and physicochemical properties
A new arylimido derivative of polyoxometalate (Bu4N)2[Mo6O17(NAr)2] [Ar = 2,6-(CH3)2C6H3]: Synthesis, structure and physicochemical properties
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DOI：
10.1016/j.ica.2005.07.020
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发表时间：
2006-01
影响因子：
2.8
通讯作者：
Yunfeng Qiu;Lin Xu;Guang-gang Gao;Wenju Wang;Fengyan Li
中科院分区：
文献类型：
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作者：
Yunfeng Qiu;Lin Xu;Guang-gang Gao;Wenju Wang;Fengyan Li
以α-八钼酸与2，6-二甲基苯胺为脱水剂，合成了一种新型的六钼酸盐双官能团芳亚胺衍生物(Bu4N)2[Mo6O17(NaR)2][Ar=2，6-(CH3)2C6H3](1)，其中两个2，6-二甲基苯胺基团在顺式位置上与六钼酸根键合。强的非典型C-H⋯O氢键的存在对化合物1的晶体结构稳定起着重要作用。荧光光谱结果表明，2，6-二甲基苯胺分子与六钼酸盐形成的共价键可以有效地猝灭2，6-二甲基苯胺分子的荧光强度，荧光猝灭率为87.7%。热分析结果表明，两个取代的2，6-(CH3)2C6H3分子在不同的温度下解离，这与化合物1中不同的MON键长是一致的。与传统的多金属氧酸盐(POM)修饰电极相比，由于POM纳米粒子的不溶性，1-CPE在500次循环中表现出显著的稳定性，这在实际应用中尤为重要。
A novel bifunctionalized arylimido derivative of hexamolybdate, (Bu4N)2[Mo6O17(NAr)2] [Ar=2,6-(CH3)2C6H3] (1), in which the two 2,6-dimethylaniline groups are bounded to hexamolybdate at the cis positions, was synthesized by a facile reaction of α-octamolybdate with 2,6-dimethylaniline using DCC as a dehydration agent. The existence of strong non-typical C–H⋯O hydrogen bonds plays an important role in crystal structure stabilization of compound 1. The results of fluorescence spectra show that the formation of a covalent bond between 2,6-dimethylaniline molecule and hexamolybdate could efficiently quench the fluorescence intensity of 2,6-dimethylaniline molecule, with a fluorescence quencher efficiency of 87.7%. Thermal analysis results indicate that two substituted 2,6-(CH3)2C6H3molecules bonding to the same cluster dissociated at different temperature, in well agreement with the different MoN bond length in compound 1. The electrochemical behavior of modified 1-CPE has been studied in detail. Compared with the conventional polyoxometalate (POM)-modified electrode, 1-CPE presents a merit of remarkable stability over 500 cycles due to the insolubility of the POM nanoparticles, which is especially important for practical applications.