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

DOI: 10.1039/C8CC10277E DOI Help

Authors: Joshua A. Hill (University of Oxford; Courtauld Institute of Art) , Claire A. Murray (Diamond Light Source) , Chiu C. Tang (Diamond Light Source) , Peter M. M. Thygesen (University of Oxford) , Amber L. Thompson (University of Oxford) , Andrew Goodwin (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Communications , VOL 318

State: Published (Approved)
Published: April 2019
Diamond Proposal Number(s): 11544 , 9981

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.

Subject Areas: Chemistry, Materials


Instruments: I11-High Resolution Powder Diffraction , I19-Small Molecule Single Crystal Diffraction