Role of entropic effects in controlling the polymorphism in formate ABX3 metal–organic frameworks

Gregor Kieslich; Shohei Kumagai; Keith T. Butler; Takuro Okamura; Christopher H. Hendon; Shijing Sun; Masahiro Yamashita; Aron Walsh; Anthony K. Cheetham

doi:10.1039/C5CC06190C

Role of entropic effects in controlling the polymorphism in formate ABX₃ metal–organic frameworks†

Gregor Kieslich,‡*^a Shohei Kumagai,‡^abc Keith T. Butler,‡^d Takuro Okamura,^b Christopher H. Hendon,^d Shijing Sun,^a Masahiro Yamashita,^bce Aron Walsh^d and Anthony K. Cheetham*^a

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* Corresponding authors

^a Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK
E-mail: gk354@cam.ac.uk, akc30@cam.ac.uk

^b Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai 980-8578, Japan

^c WPI-Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

^d Centre for Sustainable Chemical Technologies and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK

^e CREST, JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan

Abstract

Polymorphism in formate-based dense metal–organic frameworks with the general formula ABX₃ is predicted by quantum chemical calculations and confirmed experimentally. In particular [NH₃NH₂]Zn(HCOO)₃ crystallizes in two different polymorphs, a perovskite-like framework and a chiral structure with hexagonal channels. A detailed thermodynamic analysis reveals that both structures are very close in free energy and that entropy driven effects are responsible for stabilizing the channel structure.

This article is part of the themed collection: In celebration of Tony Cheetham’s 70th birthday

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DOI: https://doi.org/10.1039/C5CC06190C
Article type: Communication
Submitted: 23 Jul 2015
Accepted: 01 Sep 2015
First published: 01 Sep 2015
This article is Open Access

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Chem. Commun., 2015,51, 15538-15541

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Role of entropic effects in controlling the polymorphism in formate ABX₃ metal–organic frameworks

G. Kieslich, S. Kumagai, K. T. Butler, T. Okamura, C. H. Hendon, S. Sun, M. Yamashita, A. Walsh and A. K. Cheetham, Chem. Commun., 2015, 51, 15538 DOI: 10.1039/C5CC06190C

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Chemical Communications