Interfacial charge transfer in a functionalized polyoxotitanate cluster
Interfacial charge transfer in a functionalized polyoxotitanate cluster
复制标题
DOI：
10.1016/j.ica.2016.01.017
复制
发表时间：
2016-03
影响因子：
2.8
通讯作者：
Jie Hou;Qun Zhang;Yufei Wu;Yuliang Liu;Lin Du;C. Tung;Yifeng Wang
中科院分区：
文献类型：
--
作者：
Jie Hou;Qun Zhang;Yufei Wu;Yuliang Liu;Lin Du;C. Tung;Yifeng Wang
理解染料/二氧化钛界面上的电荷转移过程通常是用儿茶酚/二氧化钛体系来模拟的。然而，它确实需要精确的结构信息。为了在分子水平上模拟染料/二氧化钛体系，本文报道了以3，5-二叔丁基儿茶酚(DTBC)为官能团的新型钛氧簇合物[Ti4O(OIPR)6(DTBC)4](1)的合成和结构。紫外-可见光谱、电子自旋共振、X-射线光电子能谱和密度泛函理论计算表明，1具有Ti(Ⅲ)的性质，这是由于苯环上的π电子向Ti3d轨道的大量电荷转移所致。目前的精确结构和电荷转移机制有助于更好地理解发色团与半导体表面的结合以及染料/二氧化钛界面的电荷转移。
Understanding the charge transfer processes at the dye/TiO2interface is often modeled using catechol/TiO2systems. However, it indeed require precise structural information. In order to simulate the dye/TiO2systems at a molecular level, herein we report the synthesis and structure of a novel titanium oxo-cluster [Ti4O(OiPr)6(DTBC)4] (1) functionalized with 3,5-di-tert-butylcatechol (DTBC). UV–Vis spectroscopy, electron spin resonance (ESR), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations show that1exhibits property of Ti(III) which is caused by substantial charge transfer from the π electrons of the benzene rings to Ti3d orbitals. The present precise structure and charge transfer mechanism help to better understand chromophore binding to semiconductor surfaces and charge transfer at the dye/TiO2interfaces.