In this study, we systematically investigated the phase diversity and crystallization pathways of the FABr excessive regions of two ternary systems of FABr-PbBr-DMF and FABr-PbBr-DMSO (where FA-formamidinium cations, DMF-dimethylformamide and DMSO-dimethyl sulfoxide solvents). In these systems, a new FAPbBr phase with a structure containing chains of vertex-connected PbBr octahedra is discovered, and its crystal structure is refined. We experimentally assess fundamental information on differences in the mechanisms of crystallization process in FABr-PbBr-DMF and FABr-PbBr-DMSO systems and determine possible pathways of crystallization of hybrid perovskites.
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