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

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

59 Citations (Scopus)

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.

Original language	English
Pages (from-to)	15538-15541
Number of pages	4
Journal	Chemical Communications
Volume	51
Issue number	85
DOIs	https://doi.org/10.1039/c5cc06190c
Publication status	Published - 2015

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry.

All Science Journal Classification (ASJC) codes

Catalysis
Electronic, Optical and Magnetic Materials
Ceramics and Composites
Chemistry(all)
Surfaces, Coatings and Films
Metals and Alloys
Materials Chemistry

Access to Document

10.1039/c5cc06190c

Cite this

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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.",

author = "Gregor Kieslich and Shohei Kumagai and Butler, {Keith T.} and Takuro Okamura and Hendon, {Christopher H.} and Shijing Sun and Masahiro Yamashita and Aron Walsh and Cheetham, {Anthony K.}",

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AU - Kieslich, Gregor

AU - Kumagai, Shohei

AU - Butler, Keith T.

AU - Okamura, Takuro

AU - Hendon, Christopher H.

AU - Sun, Shijing

AU - Yamashita, Masahiro

AU - Walsh, Aron

AU - Cheetham, Anthony K.

PY - 2015

Y1 - 2015

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AB - 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.

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