The Effect on the Luminescent Properties in Lanthanide-Titanium OXO Clusters
The Effect on the Luminescent Properties in Lanthanide-Titanium OXO Clusters
复制标题
镧系钛氧化团簇发光性能的影响
DOI：
10.1021/acs.inorgchem.9b01223
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发表时间：
2019
影响因子：
4.6
通讯作者：
Zheng Lan-Sun
中科院分区：
文献类型：
--
作者：
Zhao Ya-Rui;Zheng Hao;Chen Liu-Qing;Chen Hui-Jun;Kong Xiang-Jian;Long La-Sheng;Zheng Lan-Sun
Two lanthanide–titanium oxo clusters (LTOCs), formulated as [Eu3Ti3(μ3-O)2(μ3-OH)(CH3O)2(Ac)2(CH3OH)(tbba)12]·CH3OH (1) and [Eu6Ti8(μ3-O)13(μ2-OH)(μ3-OCH3)2(μ2-OCH3)2(H2O)(CH3OH)2(tbba)19]·Htbba·10H2O (2), were synthesized through the solvothermal reaction of 4-tert-butylbenzoate ligand, Eu(Ac)3·3H2O, and Ti(OiPr)4in methanol. Single-crystal structural analysis reveals that1crystallized in the orthorhombic space groupPnn2, and2crystallized in the triclinic space groupP1. Structurally, the core of1can be viewed as a coplanar unit of [Eu3Ti3(μ3-O)2(μ3-OH)]16+formed through each μ3-O2–and μ3-OH–bridging one Ti4+and two Eu3+ions, while that of2can be viewed as two units of [Eu3Ti3(μ3-O)3(μ2-O)4(μ2-OCH3)2(CH3OH)]5+and [Eu3Ti5(μ3-O)6(μ2-OH)(μ3-OCH3)2(H2O)(CH3OH)]14+connected through four μ2-O units from the [Eu3Ti3(μ3-O)3(μ2-O)4(μ2-OCH3)2(CH3OH)]5+unit to respectively coordinate two Eu3+and two Ti4+ions from the [Eu3Ti5(μ3-O)6(μ2-OH)(μ3-OCH3)2(H2O)(CH3OH)]14+unit. Measurement of their luminescence properties shows that the luminescence lifetime and quantum yield are 1212 μs and 69.6% for1and 857 μs and 56.2% for2. When F–was introduced into1in a molar ratio of F–to1of 1:3, its quantum yield was increased 1.3 times, and the lifetime increased from 1.2 to 1.4 ms. However, no obvious enhancement in the emission intensity was observed in2; even the molar ratio of F–to2is in the range from 2 to 1/4. Investigation on the structures of1and2reveals that the luminescence lifetime and quantum yield in1is significantly larger than that in2are attributed to the vibration of the nonradiative O–H vibration groups in1being significantly smaller than that in2.
