Stabilization and Solvent Driven Crystal-to-Crystal Transition between New Bismuth Halides

Ramjee Kandel; Gabriele Schatte; Grace Cheng; Calvin Palmer; Diane Beauchemin; Peng L Wang

doi:10.1021/acs.inorgchem.0c00521

Stabilization and Solvent Driven Crystal-to-Crystal Transition between New Bismuth Halides

Inorg Chem. 2020 May 18;59(10):7049-7055. doi: 10.1021/acs.inorgchem.0c00521. Epub 2020 May 5.

Authors

Ramjee Kandel^{1

2}, Gabriele Schatte¹, Grace Cheng¹, Calvin Palmer¹, Diane Beauchemin¹, Peng L Wang^{1

2}

Affiliations

¹ Department of Chemistry, Queen's University, Kingston, Ontario Canada, K7L 3N6.
² Arthur B. McDonald Canadian Astroparticle Physics Research Institute, Queen's University, Kingston, Ontario Canada, K7L 3N6.

PMID: 32369351
DOI: 10.1021/acs.inorgchem.0c00521

Abstract

The investigations of bismuth halide chemistry in DMSO/MeOH solutions led to the discovery of a new solvent-stabilized compound with a chemical formula of Cs₃BiBr₆·3DMSO. In addition, a new phase of Cs₃BiBr₆ was generated as a result of a crystal-to-crystal transition driven by the change in the solvent composition. The solvent stabilized Cs₃BiBr₆·3DMSO adopts an orthorhombic P2₁2₁2₁ type crystal structure with unit cell dimension of a = 13.6160(6) Å, b = 14.4359(8) Å, and c = 14.6487(7) Å. Bulk single crystals of Cs₃BiBr₆·3DMSO with average size of 4.5 × 3.5 × 3.5 mm³ were grown by the antisolvent crystal growth method. With the change of the solvent composition from 2:1 DMSO: MeOH to 1:1 DMSO: MeOH, the single crystals of Cs₃BiBr₆·3DMSO underwent a crystal-to-crystal transition yielding another structurally distinct Cs₃BiBr₆ phase, with a tetragonal P4₂/m type structure and unit cell dimensions of a = 9.8394(5) Å, b = 9.8394(5) Å, and c = 8.0950(6) Å. Both compounds exhibit isolated BiBr₆ octahedral resembling the structures of the zero-dimensional (0D) perovskites.