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Inorganic Co-Crystal Formation and Thermal Disproportionation in a Dicyanometallate 'Superperovskite'

preprint
submitted on 02.01.2019 and posted on 03.01.2019 by Joshua A. Hill, Claire A. Murray, Chiu C. Tang, Peter M. M. Thygesen, Amber L. Thompson, Andrew Goodwin

We report the synthesis, crystal structure, and thermally- driven phase transformation of the dicyanometallate super- perovskite co-crystal [NBu4]Mn[Au(CN)2]3·[NBu4]ClO4. This phase is understandable in terms of the conventional ABX3 perovskite structure type, but with the NBu+4 A-site cation displaced onto the perovskite cage face and 1-dimensional AX′ chains included within framework pores opened up by these displacements. On heating to 380K, the co-crystal disproportionates into its two inorganic components: a bcs-structured ABX3 phase and [NBu4 ]ClO4 . This system illustrates a new type of structural and phase complexity accessible to dicyanometallate perovskites.

History

Email Address of Submitting Author

andrew.goodwin@chem.ox.ac.uk

Institution

University of Oxford

Country

UK

ORCID For Submitting Author

0000-0001-9231-3749

Declaration of Conflict of Interest

No conflict of interest

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