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来自铟基金属有机框架的高量子产率纯蓝光发射和快速质子传导。

High quantum yield pure blue emission and fast proton conduction from an indium-metal-organic framework.

作者信息

Zhai Lu, Yu Jing-Wei, Zhang Jin, Zhang Wen-Wei, Wang Lifeng, Ren Xiao-Ming

机构信息

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry & Molecular Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, P. R. China.

出版信息

Dalton Trans. 2019 Aug 28;48(32):12088-12095. doi: 10.1039/c9dt02472g. Epub 2019 Jul 25.

Abstract

A multifunctional material, with two or more types of functionalities in a single material, might give new phenomena and novel applications. Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) can be utilized as a highly versatile and tunable platform for exploring multifunctional materials. In this study, an extra thermally stable indium-MOF (1) was synthesized via self-assembly of 1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid (HEBTC) with an indium salt under solvothermal conditions. MOF 1 crystallizes in a tetragonal space group P4/mmm and shows a three-dimensional (3D) anionic framework with one-dimensional (1D) channels along the c-axis direction, and charge-balancing [(CH)NH] cations together with lattice DMF and water molecules are accommodated in channels. This multifunctional MOF emits pure blue luminescence under ambient conditions, arising from the π* →π electron transition in EBTC, with CIE coordinates of (0.16, 0.07), and shows the highest quantum yield of 61.4% among indium-MOFs. Alternatively, 1 features fast proton conductivity with σ = 3.49 × 10 S cm at 25 °C and 99% RH, attributed to the efficiently synergistic proton transfer in the H-bond networks constructed by [NH(CH)] cations, lattice water molecules in channels and carboxylate groups in the framework. The notable level of performance of 1, combined with good hydrolytic and extra thermal stability, offers great opportunities for its future applications, and it may behave as a kind of promising multifunctional MOF material.

摘要

一种在单一材料中具有两种或更多类型功能的多功能材料,可能会带来新的现象和新颖的应用。金属有机框架(MOF)或多孔配位聚合物(PCP)可作为探索多功能材料的高度通用且可调谐的平台。在本研究中,通过1,1'-乙炔苯-3,3',5,5'-四羧酸(HEBTC)与铟盐在溶剂热条件下自组装合成了一种具有额外热稳定性的铟-MOF(1)。MOF 1结晶于四方空间群P4/mmm,呈现出沿c轴方向具有一维(1D)通道的三维(3D)阴离子框架,电荷平衡的[(CH)NH]阳离子以及晶格DMF和水分子容纳在通道中。这种多功能MOF在环境条件下发出纯蓝色荧光,源于EBTC中的π*→π电子跃迁,CIE坐标为(0.16, 0.07),并且在铟-MOF中显示出最高61.4%的量子产率。此外,1在25°C和99%相对湿度下具有快速质子传导率,σ = 3.49×10 S cm,这归因于由[NH(CH)]阳离子、通道中的晶格水分子和框架中的羧酸根基团构建的氢键网络中高效的协同质子转移。1的显著性能水平,再加上良好的水解稳定性和额外的热稳定性,为其未来应用提供了巨大机遇,它可能成为一种有前景的多功能MOF材料。

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