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在环境条件下,一种具有1,1'-乙炔苯-3,3',5,5'-四羧酸酯配体的二维铅(II)配位聚合物发出强烈的绿色磷光。

Intense greenish phosphorescence emission under ambient conditions in a two-dimensional lead(ii) coordination polymer with a 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate ligand.

作者信息

Liu Xiao, Zhai Lu, Zhang Wen-Wei, Zuo Jin-Lin, Yang Zhu-Xi, Ren Xiao-Ming

机构信息

State Key Laboratory of Materials-Oriented Chemical Engineering and College of Chemistry & Molecular Engineering, Nanjing Tech University, Nanjing 210009, P. R. China.

State Key Lab & Coordination Chemistry Institute, Nanjing University, Nanjing 210093, P. R. China.

出版信息

Dalton Trans. 2017 Jun 28;46(24):7953-7959. doi: 10.1039/c7dt01626c. Epub 2017 Jun 12.

DOI:10.1039/c7dt01626c
PMID:28604882
Abstract

In this study, a new two-dimensional Pb-based coordination polymer (CP), [Pb(EBTC)(DMSO)] (1), where HEBTC is 1,1'-ethynebenzene 3,3',5,5'-tetracarboxylic acid, was synthesized under solvothermal conditions. Structural analysis reveals that 1 crystallizes in the monoclinic space group C2/m, where two crystallographically different Pb ions show a coordination geometry of bicapped trigonal prisms that are connected to a double-chain by the EBTC ligands through carboxylate groups along the b-axis direction, and where successive double chains are held together to form a 2D layer via the Pb1 and Pb2 bicapped trigonal prisms sharing one edge or a triangle face along the c-axis direction. Interestingly, CP 1 emitted intense and long-lived greenish phosphorescence in the solid state at ambient conditions, with a quantum yield of 1.5% and a phosphorescence lifetime of 4.17 ms, and the emission mainly arose from the electron transition within the π-type orbitals of the EBTC ligand. The emission bands assignment and photophysical process were further discussed according to the calculation of both the electronic band structures and density of states. This study gives a fresh impetus to achieve coordination polymer-based long-lived phosphorescence materials under ambient conditions.

摘要

在本研究中,一种新型二维铅基配位聚合物(CP),[Pb(EBTC)(DMSO)](1),其中HEBTC为1,1'-乙炔基苯3,3',5,5'-四羧酸,在溶剂热条件下合成。结构分析表明,1结晶于单斜空间群C2/m,其中两个晶体学上不同的铅离子呈现双帽三角棱柱的配位几何构型,它们通过EBTC配体的羧基沿b轴方向连接成双链,并且连续的双链通过Pb1和Pb2双帽三角棱柱沿c轴方向共享一条边或一个三角形面而结合在一起形成二维层。有趣的是,CP 1在环境条件下的固态中发出强烈且长寿命的绿色磷光,量子产率为1.5%,磷光寿命为4.17 ms,且发射主要源于EBTC配体π型轨道内的电子跃迁。根据电子能带结构和态密度的计算,进一步讨论了发射带归属和光物理过程。本研究为在环境条件下实现基于配位聚合物的长寿命磷光材料提供了新的推动力。

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