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Updated: Apr 4, 2026

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
Role of entropic effects in controlling the polymorphism in formate ABX3 metal-organic frameworks
Gregor Kieslich1, Shohei Kumagai, Keith T Butler
1Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK. gk354@cam.ac.uk akc30@cam.ac.uk.
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.
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