College of Chemistry and Chemical Engineering, Henan Province Key Laboratory of Utilization of Non-metallic Mineral in the South of Henan, Xinyang Normal University, Xinyang 464000, China.
Dalton Trans. 2018 Jun 19;47(24):8158-8163. doi: 10.1039/c8dt01844h.
Four phenylphosphonate-stabilized titanium-oxo clusters with varying functional ligands, namely, [Ti8(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)8(O3PC6H5)4(cat)2] (cat = catecholate), [Ti8(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)8(O3PC6H5)4(O2C10H6)2] (O2C10H6 = naphthalene-2,3-diolate), [Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(O3PC6H5)2(4-DMAB)2] (4-DMAB = 4-dimethylaminobenzoate), and [Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(O3PC6H5)2(4-CBA)2] (4-CBA = 4-cyanobenzoate) were synthesized and structurally characterized. The introduction of catecholate ligands effectively extended the visible absorption region up to 670 nm and reduced the band gap to 2.1 eV. DFT calculations revealed that the ligand-based energy levels could effectively modify the band structure of titanium-oxo clusters. The ligand-to-core charge transfer (LCCT) transition from the functional ligands to the cluster core is responsible for the low-energy charge transfer states. Photoelectrochemical and photocatalytic experiments show that functional ligands have significant influence on the physicochemical properties of titanium-oxo clusters.
四个带有不同功能配体的苯膦酸稳定的钛氧簇，分别为[Ti8(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)8(O3PC6H5)4(cat)2]（cat = 儿茶酚）、[Ti8(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)8(O3PC6H5)4(O2C10H6)2]（O2C10H6 = 萘-2,3-二醇）、[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(O3PC6H5)2(4-DMAB)2]（4-DMAB = 4-二甲氨基苯甲酸酯）和[Ti6(μ3-O)2(μ2-O)2(μ2-OiPr)4(OiPr)6(O3PC6H5)2(4-CBA)2]（4-CBA = 4-氰基苯甲酸酯）被合成并进行了结构表征。儿茶酚配体的引入有效地将可见吸收区域扩展至 670nm，并将带隙降低至 2.1eV。DFT 计算表明，配体能级可以有效地修饰钛氧簇的能带结构。来自功能配体到簇核的配体-核电荷转移（LCCT）跃迁负责低能量电荷转移态。光电化学和光催化实验表明，功能配体对钛氧簇的物理化学性质有显著影响。
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