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A 4-dimethylaminobenzoate-functionalized Ti6-oxo cluster with a narrow band gap and enhanced photoelectrochemical activity: a combined experimental and computational study
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-08-25 00:00:00 , DOI: 10.1039/c7dt02650a Hai-Ting Lv 1, 2, 3, 4, 5 , Ying Cui 1, 2, 3, 4, 5 , Yu-Min Zhang 1, 2, 3, 4, 5 , Hua-Min Li 1, 2, 3, 4, 5 , Guo-Dong Zou 1, 2, 3, 4, 5 , Rui-Huan Duan 5, 6, 7, 8 , Jun-Tao Cao 1, 2, 3, 4, 5 , Qiang-Shan Jing 1, 2, 3, 4, 5 , Yang Fan 1, 2, 3, 4, 5
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-08-25 00:00:00 , DOI: 10.1039/c7dt02650a Hai-Ting Lv 1, 2, 3, 4, 5 , Ying Cui 1, 2, 3, 4, 5 , Yu-Min Zhang 1, 2, 3, 4, 5 , Hua-Min Li 1, 2, 3, 4, 5 , Guo-Dong Zou 1, 2, 3, 4, 5 , Rui-Huan Duan 5, 6, 7, 8 , Jun-Tao Cao 1, 2, 3, 4, 5 , Qiang-Shan Jing 1, 2, 3, 4, 5 , Yang Fan 1, 2, 3, 4, 5
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Organic donor–π-bridge-acceptor (D–π-A) dyes with arylamines as an electron donor have been widely used as photosensitizers for dye-sensitized solar cells (DSSCs). However, titanium-oxo clusters (TOCs) functionalized with this kind of D–π-A structured dye-molecule have rarely been explored. In the present study, the 4-dimethylaminobenzoate-functionalized titanium-oxo cluster [Ti6(μ3-O)6(OiPr)6(DMABA)6]·2C6H5CH3 (DMABA = 4-dimethylaminobenzoate) was synthesized and structurally characterized by single-crystal X-ray diffraction. For comparison, two other Ti6-oxo clusters, namely [Ti6(μ3-O)6(OiPr)6(AD)6] (AD = 1-adamantanecarboxylate) and [Ti6(μ3-O)2(μ2-O)(μ2-OiPr)4(OiPr)10(DMM)2] (DMM = dimethylmalonate), were also studied. The DMABA-functionalized cluster exhibits a remarkably reduced band gap of ∼2.5 eV and much enhanced photocurrent response in comparison with the other two clusters. The electronic structures and electronic transitions of the clusters were studied by DFT and TDDFT calculations. The computational results suggest that the low-energy transitions of the DMABA-functionalized cluster have a substantial charge-transfer character arising from the DMABA → {Ti6} cluster core ligand-to-core charge transfer (LCCT), along with the DMABA-based intra-ligand charge transfer (ILCT). These low-energy charge transfer transitions provide efficient electron injection pathways for photon-to-electron conversion.
中文翻译：
具有窄带隙和增强的光电化学活性的4-二甲基氨基苯甲酸酯官能化的Ti 6-氧簇：结合实验和计算研究
以芳基胺为电子给体的有机供体-π-桥-受体（D-π-A）染料已被广泛用作染料敏化太阳能电池（DSSC）的光敏剂。然而，很少有人探索用这种D–π-A结构染料分子功能化的钛-氧代簇（TOC）。在本研究中，4-二甲基氨基-官能化钛-氧簇钛[Ti 6（μ 3 -O）6（OiPr）6（DMABA）6 ]·2C 6 H ^ 5 CH 3（DMABA = 4-二甲基氨基）合成并且在结构上通过单晶X射线衍射表征。为了比较，另外两个Ti 6 -oxo团簇，即[Ti 6（μ 3 -O）6（OiPr）6（AD）6 ]（AD = 1-金刚烷）和钛[Ti 6（μ 3 -O）2（μ 2 -O）（μ 2 -OiPr）4（OiPr）10（DMM）2]（DMM =丙二酸二甲酯）也进行了研究。与其他两个群集相比，DMABA功能化的群集显示出〜2.5 eV的带隙显着减小，并且光电流响应大大增强。通过DFT和TDDFT计算研究了团簇的电子结构和电子跃迁。计算结果表明，DMABA功能化簇的低能跃迁具有重要的电荷转移特性，这是由于DMABA→{Ti 6 }簇核心配体-核心电荷转移（LCCT）以及DMABA-基于配体内电荷转移（ILCT）。这些低能量的电荷转移跃迁为光子到电子的转换提供了有效的电子注入途径。
更新日期：2017-09-20
中文翻译：
具有窄带隙和增强的光电化学活性的4-二甲基氨基苯甲酸酯官能化的Ti 6-氧簇：结合实验和计算研究
以芳基胺为电子给体的有机供体-π-桥-受体（D-π-A）染料已被广泛用作染料敏化太阳能电池（DSSC）的光敏剂。然而，很少有人探索用这种D–π-A结构染料分子功能化的钛-氧代簇（TOC）。在本研究中，4-二甲基氨基-官能化钛-氧簇钛[Ti 6（μ 3 -O）6（OiPr）6（DMABA）6 ]·2C 6 H ^ 5 CH 3（DMABA = 4-二甲基氨基）合成并且在结构上通过单晶X射线衍射表征。为了比较，另外两个Ti 6 -oxo团簇，即[Ti 6（μ 3 -O）6（OiPr）6（AD）6 ]（AD = 1-金刚烷）和钛[Ti 6（μ 3 -O）2（μ 2 -O）（μ 2 -OiPr）4（OiPr）10（DMM）2]（DMM =丙二酸二甲酯）也进行了研究。与其他两个群集相比，DMABA功能化的群集显示出〜2.5 eV的带隙显着减小，并且光电流响应大大增强。通过DFT和TDDFT计算研究了团簇的电子结构和电子跃迁。计算结果表明，DMABA功能化簇的低能跃迁具有重要的电荷转移特性，这是由于DMABA→{Ti 6 }簇核心配体-核心电荷转移（LCCT）以及DMABA-基于配体内电荷转移（ILCT）。这些低能量的电荷转移跃迁为光子到电子的转换提供了有效的电子注入途径。
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