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Type: Journal article
Title: Hydrogen adsorption in azolium and metalated N-heterocyclic carbene containing MOFs
Author: Capon, P.
Burgun, A.
Coghlan, C.
Crees, R.
Doonan, C.
Sumby, C.
Citation: CrystEngComm, 2016; 18(37):7003-7010
Publisher: Royal Society of Chemistry
Issue Date: 2016
ISSN: 1466-8033
Statement of
Patrick K. Capon, Alexandre Burgun, Campbell J. Coghlan, Rachel S. Crees, Christian J. Doonan and Christopher J. Sumby
Abstract: Azolium and metalated N-heterocyclic carbene (NHC) functionalised metal–organic frameworks (MOFs) have been investigated as adsorbents and heterogenous catalysts. Here we describe the structures of two sets of 1D polymeric structures, {[M2(μ2-HCOO)(HL)2](NO3)·xDMF}n (M = Zn, x = 1, 1; Cu, x = 1.75, 2) and {[M3(HL)4(H2O)4](NO3)2·xDMF}n (M = Co, x = 2.75, 3; Mg, x = 0, 4; Mn, x = 1.5, 5), prepared from reactions of 1,3-bis(3-carboxyphenyl)-1H-imidazol-3-ium bromide (H3LBr) with M(NO3)2·xH2O (M = Zn, Cu, Co and Mg) and MnCl2·4H2O. These pack as porous and non-porous 3D materials, respectively. In the case of the known Zn(II) material 1, which we reveal to be porous, we also report metalation of the NHC precursor concomitant with framework synthesis to give {[Zn2(μ2-HCOO)(HL)1.6(L–Cu–Br)0.4](NO3)0.6·0.75DMF}n (1-Cu). Compounds 1, 2, and 1-Cu show H2 adsorption enthalpies of −9.9, −9.1, and −9.7 kJ mol−1 respectively, and allow the effect of micropores decorated with charged imidazolium moieties, or NHC–CuBr entities, on H2 adsorption to be probed.
Rights: This journal is © The Royal Society of Chemistry 2016
DOI: 10.1039/c6ce01549b
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