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

Author affiliations

* 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

Supplementary files

Article information

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

Download Citation

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

Permissions

Request permissions

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

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.

Chemical Communications