Wang Sheng, Su Hu-Chao, Yu Lan, Zhao Xiao-Wei, Qian Li-Wen, Zhu Qin-Yu, Dai Jie
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
Dalton Trans. 2015 Jan 28;44(4):1882-8. doi: 10.1039/c4dt02968b.
Two 9-anthracenecarboxylate (9-AC) coordinated heterometallic TOC compounds, [Ln2Ti10O14(ClO4)2(O(i)Pr)14(9-AC)2(CH3CN)2]·2H2O, Ln = Nd 1() and Eu (2), along with two benzoate (bza) analogues, [Ln2Ti10O14(ClO4)2(O(i)Pr)14(bza)2(HO(i)Pr)2], Ln = Nd (3) and Eu (4), were prepared by one step in situ solvothermal synthesis, and characterized by single crystal analysis. To date, only about ten lanthanum-titanium oxo clusters have been reported. Except for two Ti28 clusters, the compounds are all small clusters (Ti ≤ 4). The cluster structures of 1-4 adopt a Ti10Ln2 core structure with pseudo-Ci symmetry, which is similar to the fundamental structure of Ti12 clusters. Furthermore, except for their structures, the properties of lanthanum-titanium oxo clusters have never been studied. Herein, the fluorescence properties of these compounds are studied in detail. The metal centered emission of Eu(III) is completely quenched by 9-AC due to the lower triplet energy of the coordinated ligand. Enhanced ligand centered fluorescence is found for 2 in comparison with that of 1.
通过一步原位溶剂热合成法制备了两种9-蒽甲酸酯（9-AC）配位的异金属钛氧簇化合物，[Ln₂Ti₁₀O₁₄(ClO₄)₂(O(i)Pr)₁₄(9-AC)₂(CH₃CN)₂]·2H₂O，Ln = Nd 1（）和Eu（2），以及两种苯甲酸酯（bza）类似物，[Ln₂Ti₁₀O₁₄(ClO₄)₂(O(i)Pr)₁₄(bza)₂(HO(i)Pr)₂]，Ln = Nd（3）和Eu（4），并通过单晶分析对其进行了表征。迄今为止，仅报道了约十种镧 - 钛氧簇。除了两个Ti₂₈簇外，这些化合物都是小簇（Ti≤4）。1-4的簇结构采用具有假Ci对称性的Ti₁₀Ln₂核心结构，这与Ti₁₂簇的基本结构相似。此外，除了它们的结构外，镧 - 钛氧簇的性质从未被研究过。在此，详细研究了这些化合物的荧光性质。由于配位配体的三重态能量较低，Eu(III)的金属中心发射被9-AC完全猝灭。与1相比，发现2的配体中心荧光增强。
