Tilt and shift polymorphism in molecular perovskites

Burger, S., Grover, S., Butler, K. T., Bostrom, H. L. B., Grau-Crespo, R. ORCID: https://orcid.org/0000-0001-8845-1719 and Kieslich, G. (2021) Tilt and shift polymorphism in molecular perovskites. Materials Horizons, 2021 (9). pp. 2444-2450. ISSN 2051-6355 doi: 10.1039/D1MH00578B

Abstract/Summary

Molecular perovskites, i.e. ABX3 coordination polymers with a perovskite structure, are a chemically diverse material platform for studying fundamental and applied materials properties such as barocalorics and improper ferroelectrics. Compared to inorganic perovskites, the use of molecular ions on the A- and X-site of molecular perovskites leads to new geometric and structural degrees of freedom. In this work we introduce the concept of tilt and shift polymorphism, categorising irreversible perovskite-to-perovskite phase transitions in molecular perovskites. As a model example we study the new molecular perovskite series [(nPr)3(CH3)N]M(C2N3)3 with M = Mn2+, Co2+, Ni2+, and nPr = n-propyl, where different polymorphs crystallise in the perovskite structure but with different tilt systems depending on the synthetic conditions. Tilt and shift polymorphism is a direct ramification of the use of molecular building units in molecular perovskites and as such is unknown for inorganic perovskites. Given the role of polymorphism in materials science, medicine and mineralogy, and more generally the relation between physicochemical properties and structure, the concept introduced herein represents an important step in classifying the crystal chemistry of molecular perovskites and in maturing the field.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/99127
Identification Number/DOI	10.1039/D1MH00578B
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Uncontrolled Keywords	perovskites; DFT; barocalorics
Publisher	Royal Society of Chemistry
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