Organic–inorganic hybrid perovskites are categorized as multifunctional materials due to their structural designability and functional diversity. Herein, two manganese-based organic–inorganic perovskite type compounds [Me3NNH2]MnCl3 (1) and [(CH3)3NCH2CH2F]2MnCl4 (2) were synthesized by reactions of trimethylhydrazine iodide and (fluoromethyl)trimethylammonium bromide with MnCl2 in concentrated hydrochloric acid aqueous solution. Differential scanning calorimetry (DSC) and dielectric measurements revealed that compounds 1 and 2 undergo reversible phase transitions at about 327 K and 352 K, respectively. Significantly, under the excitation of 365 nm, compounds 1 and 2 emit green and red luminescence, which originate from the octahedral [MnCl6] and tetrahedral [MnCl4] moieties.
