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镧系收缩调控的 salen 型镧系配合物结构及其发光性能的系统研究。

Systematic study on the structures of salen type lanthanide complexes tuned by lanthanide contraction and corresponding luminescence.

机构信息

Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, P. R. China.

出版信息

Dalton Trans. 2013 Jul 14;42(26):9482-9. doi: 10.1039/c3dt50534k. Epub 2013 May 10.

Abstract

Two types of N,N'-bis(salicylidene)-1,3-propanediamine (H2L) lanthanide complexes, viz. [Ln(NO3)3(H2L)2]·0.2CH3OH [Ln = La (1), Ce (2) and Pr (3)] and [Ln(NO3)3(H2L)2]2·CH2Cl2·CH3OH [Ln = Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Yb (9)], have been isolated by reactions of H2L with Ln(NO3)3·6H2O. X-ray crystallographic and PXRD analysis reveal that 1-3 are isomorphic possessing a novel one-dimensional (1D) ladder-like double-chain structure. Complexes 4-9 are isostructural exhibiting a discrete dinuclear structure. Luminescent analysis reveals the lanthanide ion and ligand-centered co-luminescence for 5, 6 and 8, which are attributed to the incomplete energy transfer from the triplet state of H2L to the resonance energy level of the corresponding Ln(iii) ion. Further, the characteristic near infrared (NIR) luminescence of Nd(iii) and Yb(iii) ions for complexes 4 and 9 have been revealed.

摘要

两种类型的 N,N'-双(水杨醛)-1,3-丙二胺(H2L)镧系元素配合物,即 [Ln(NO3)3(H2L)2]·0.2CH3OH [Ln = La(1)、Ce(2)和 Pr(3)] 和 [Ln(NO3)3(H2L)2]2·CH2Cl2·CH3OH [Ln = Nd(4)、Sm(5)、Eu(6)、Gd(7)、Tb(8)和 Yb(9)],是通过 H2L 与 Ln(NO3)3·6H2O 的反应得到的。X 射线晶体学和 PXRD 分析表明,1-3 是同构的,具有新颖的一维(1D)梯形双链结构。配合物 4-9 是同构的,呈现离散的双核结构。发光分析表明,5、6 和 8 中的镧系元素离子和配体中心协同发光,这归因于从 H2L 的三重态到相应 Ln(iii)离子的共振能级的不完全能量转移。此外,还揭示了配合物 4 和 9 中 Nd(iii)和 Yb(iii)离子的特征近红外(NIR)发光。

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