Issue 11, 2017

Synthetic control of coincidental formation of an N-heterocyclic carbene–copper(i) complex and imidazolium cations within metal–organic frameworks

Abstract

By changing the concentration of copper salt (Cu(ClO4)2), a two-dimensional (2D) copper paddle-wheel-based metal–organic framework (MOF) containing an imidazolium unit (Im-MOF-1 with a framework formula of [CuII(L)(NMP)](ClO4), L = 1,3-bis(4-carboxyphenyl)imidazolium and NMP = N-methyl-2-pyrrolidone) and a 3D MOF (Im-MOF-2, CuII(L)(H2O)) with aqua-bridged Cu ions as inorganic infinite secondary building units were respectively prepared. With CuCl as a copper source, another square-grid 2D MOF (Im-MOF-3, CuII(LNHC–CuICl)(NMP), LNHC = a carbene form of L) was obtained; Im-MOF-3 is isostructural with Im-MOF-1 except that its organic linker has an N-heterocyclic carbene (NHC) copper(I) complex (LNHC–CuICl). Density functional theory modeling calculations show that the NHC–CuCl complex in the organic linker of Im-MOF-3 retains the electronic properties of its molecular form, as evidenced by molecular orbital analysis.

Graphical abstract: Synthetic control of coincidental formation of an N-heterocyclic carbene–copper(i) complex and imidazolium cations within metal–organic frameworks

Supplementary files

Article information

Article type
Paper
Submitted
12 Jan 2017
Accepted
14 Feb 2017
First published
15 Feb 2017

CrystEngComm, 2017,19, 1528-1534

Synthetic control of coincidental formation of an N-heterocyclic carbene–copper(I) complex and imidazolium cations within metal–organic frameworks

H. Lee, H. Kwon, J. Sim, D. Song, Y. Kim, J. Kim, K. Kim and E. Lee, CrystEngComm, 2017, 19, 1528 DOI: 10.1039/C7CE00078B

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