Crystallization Pathways of FABr-PbBr2-DMF and FABr-PbBr2-DMSO Systems: The Comprehensive Picture of Formamidinium-Based Low-Dimensional Perovskite-Related Phases and Intermediate Solvates

In this study, we systematically investigated the phase diversity and crystallization pathways of the FABr excessive regions of two ternary systems of FABr-PbBr₂-DMF and FABr-PbBr₂-DMSO (where FA⁺—formamidinium cations, DMF—dimethylformamide and DMSO—dimethyl sulfoxide solvents). In these systems, a new FA₃PbBr₅ phase with a structure containing chains of vertex-connected PbBr₆ octahedra is discovered, and its crystal structure is refined. We experimentally assess fundamental information on differences in the mechanisms of crystallization process in FABr-PbBr₂-DMF and FABr-PbBr₂-DMSO systems and determine possible pathways of crystallization of hybrid perovskites. We show that intermediate solvate phases are not observed in the system with DMF solvent, while a number of crystalline solvates tend to form in the system with DMSO at various amounts of FABr excess.