Inorganic co-crystal formation and thermal disproportionation in a dicyanometallate 'superperovskite'

Joshua A Hill; Claire A Murray; Chiu C Tang; Peter M M Thygesen; Amber L Thompson; Andrew L Goodwin

doi:10.1039/c8cc10277e

Inorganic co-crystal formation and thermal disproportionation in a dicyanometallate 'superperovskite'

Chem Commun (Camb). 2019 May 7;55(38):5439-5442. doi: 10.1039/c8cc10277e.

Authors

Joshua A Hill¹, Claire A Murray, Chiu C Tang, Peter M M Thygesen, Amber L Thompson, Andrew L Goodwin

Affiliation

¹ Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford OX1 3QR, UK. andrew.goodwin@chem.ox.ac.uk.

PMID: 31020306
DOI: 10.1039/c8cc10277e

Abstract

We report the synthesis, crystal structure, and thermally-driven phase transformation of the dicyanometallate superperovskite 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 NBu4+ 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 380 K, 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.