Issue 4, 2022

Synthesis, structures and properties of metal–organic frameworks prepared using a semi-rigid tricarboxylate linker

Abstract

The metal–organic frameworks formed from the reaction between cadmium(II) salts and the semi-rigid 5-((carboxymethyl)amino)isophthalic acid (H3cmai) in water at 90 °C are dependent on the counter-ions, with [Cd2(Hcmai)2(H2O)2]·H2O (1), [Cd(Hcmai)(H2O)2] (2) and [Cd3(cmai)2(H2O)4]·4H2O (3) forming from the nitrate, chloride and the acetate salts, respectively. Compound 3 loses both lattice and coordinated water molecules on heating to 150 °C and is converted into [Cd3(cmai)2] (4). This reaction occurs in a single-crystal-to-single-crystal manner and was followed using variable temperature X-ray powder diffraction. The reaction of cadmium(II) nitrate with H3cmai in a mixture of water and DMF afforded [Cd6(cmai)4(H2O)9.75(DMF)2.25]·18H2O·1.5DMF (5) whereas the same reaction in water and DEF in the presence of 4,4′-bipyridine led to [Cd3(cmai)2(H2O)3]·6H2O (6). Generally, the coordination networks containing Hcmai (1–2) propagate in one or two dimensions, whereas those containing cmai (3–6) propagate in three dimensions. Use of the first row d-block salts zinc(II), copper(II) and cobalt(II) nitrate resulted in compounds [M(Hcmai)(H2O)x] (M = Zn, x = 2 (7), M = Cu, x = 1.2 (8), M = Co, x = 2 (9)), with 8 showing photocatalytic activity for the degradation of the dye rhodamine B. Finally, the reaction of zinc(II) acetate with H3cmai in water and DEF yielded [Zn2(cmai)(OH)(H2O)2]·3H2O (10). Compounds 7–10 all form two-dimensional networks.

Graphical abstract: Synthesis, structures and properties of metal–organic frameworks prepared using a semi-rigid tricarboxylate linker

Supplementary files

Article information

Article type
Paper
Submitted
27 sep. 2021
Accepted
18 des. 2021
First published
06 jan. 2022
This article is Open Access
Creative Commons BY license

CrystEngComm, 2022,24, 863-876

Synthesis, structures and properties of metal–organic frameworks prepared using a semi-rigid tricarboxylate linker

D. Rixson, G. Günay Sezer, E. Alp, M. F. Mahon and A. D. Burrows, CrystEngComm, 2022, 24, 863 DOI: 10.1039/D1CE01284C

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