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Issue 18, 2016

Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks

Author affiliations

Abstract

The synthesis of zirconium and hafnium metal–organic frameworks (MOFs) often relies on coordination modulation – the addition of competing monotopic modulators to reaction mixtures – to reproducibly generate highly crystalline material. Typically, large excesses of monocarboxylic acids such as formic, acetic and benzoic acid are applied, but access to diffraction quality single crystals, particularly of UiO-66 topology MOFs, remains troublesome. Herein, we show that amino acids, in particular L-proline, are highly efficient modulators of Zr and Hf MOFs of the UiO-66 series, with as little as four equivalents affording access to large, diffraction quality single crystals that are free of defects. Five crystal structures are reported, including MOFs which previously could not be characterised in this manner, with molecular dynamics simulations utilised to understand dynamic disorder. Additionally, a series of MOFs are characterised in depth, allowing a comparison of the thermal stabilities and porosities for Zr and Hf analogues. We also show that the protocol can be extended to microwave synthesis, and that modulating ability varies dramatically across a series of amino acids. Access to single crystals has facilitated our own in depth study of the mechanical properties of these MOFs, and we expect that our protocols will enable the discovery of new Zr and Hf MOFs as well as offer new insights into their materials properties.

Graphical abstract: Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks

Supplementary files

Article information


Submitted
18 Dec 2015
Accepted
02 Feb 2016
First published
04 Feb 2016

This article is Open Access

J. Mater. Chem. A, 2016,4, 6955-6963
Article type
Paper
Author version available

Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks

R. J. Marshall, C. L. Hobday, C. F. Murphie, S. L. Griffin, C. A. Morrison, S. A. Moggach and R. S. Forgan, J. Mater. Chem. A, 2016, 4, 6955 DOI: 10.1039/C5TA10401G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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