Hou Jin-Le, Luo Wen, Guo Yao, Zhang Ping, Yang Shen, Zhu Qin-Yu, Dai Jie
College of Chemistry, Chemical Engineering and Materials Science, Soochow University , Suzhou 215123, P. R. China.
The Key Laboratory of Rare Earth Functional Materials and Applications, Zhoukou Normal University , Zhoukou 466001, P. R. China.
Inorg Chem. 2017 Jun 5;56(11):6451-6458. doi: 10.1021/acs.inorgchem.7b00522. Epub 2017 May 24.
A unique titanium oxo cluster with a ferrocene ligand was synthesized and characterized by single crystal X-ray analysis. Six ferrocene carboxylates coordinate to a D TiO core to be a redox active cluster 1, [TiO(OPr)(OCFc)]. An analogue 2, [TiO(OPr)(OCBu)], where the redox active ferrocene group is replaced by isobutyrate, is also reported as a contrast. The six ferrocene moieties in 1 are structurally identical to give a main redox wave at E = 0.62 V in dichloromethane investigated by cyclic voltammetry. Photocurrent responses using electrodes of clusters 1 and 2 were studied, and the response properties of 1 are better than those of 2. The electronic spectra and theoretical calculations indicate that charge transfer occurs from ferrocene to Ti(IV) in 1, and the presence of the ferrocene moiety gives efficient electron excitation and charge separation. Cluster 1 is a cooperative system of TiO cluster and redox active ferrocene. Photocurrent response properties of an electrode of 1 for four saccharides, glucose, fructose, maltose, and sucrose, were tested, and only reducing sugars were responsive. The electrode of 2 is also photocurrent responsive to saccharides, but the current densities are lower than those of redox active 1.
合成了一种具有二茂铁配体的独特钛氧簇，并通过单晶X射线分析对其进行了表征。六个二茂铁羧酸盐与一个D TiO核配位，形成一个氧化还原活性簇1，即[TiO(OPr)(OCFc)]。还报道了一种类似物2，即[TiO(OPr)(OCBu)]，其中氧化还原活性二茂铁基团被异丁酸盐取代作为对比。通过循环伏安法研究发现，1中的六个二茂铁部分在结构上是相同的，在二氯甲烷中于E = 0.62 V处给出一个主要的氧化还原波。研究了使用簇1和2的电极的光电流响应，1的响应性能优于2。电子光谱和理论计算表明，在1中发生了从二茂铁到Ti(IV)的电荷转移，二茂铁部分的存在实现了有效的电子激发和电荷分离。簇1是TiO簇和氧化还原活性二茂铁的协同体系。测试了1的电极对四种糖类（葡萄糖、果糖、麦芽糖和蔗糖）的光电流响应性能，结果表明只有还原糖有响应。2的电极对糖类也有光电流响应，但电流密度低于氧化还原活性的1。
