Synthesis and Luminescent Behavior of Lead, Manganese, and Copper Containing Organic–Inorganic Metal Halides

Abstract

Organic–inorganic metal halides (OIMHs) have attracted considerable attention owing to their unique optoelectronic properties. Here, we successfully synthesized five lead, manganese and copper containing OIMHs based on 4-aminodiphenylmethane (C₁₃H₁₃N) and 4,4′-methylenedianiline (C₁₃H₁₄N₂). Among them, (C₁₃H₁₄N)₂PbCl₄ and (C₁₃H₁₄N)₂PbBr₄, both exhibiting two-dimensional frameworks, crystallize into the Pmm2 and P2₁/c space groups, respectively, and present optical band gaps of approximately 3.6 and 3.0 eV. (C₁₃H₁₄N)₂PbCl₄ demonstrates blue light emission centered at 502 nm with a substantial full width at half-maximum (fwhm) of 180 nm and a Stokes shift of 182 nm, originating from self-trapped exciton emission. In contrast, (C₁₃H₁₄N)₂PbBr₄ displays blue photoluminescence characterized by a fwhm of 26 nm and an emission peak at 417 nm, corresponding to free exciton emission. Additionally, we investigated three zero-dimensional OIMHs: (C₁₃H₁₄N)₄MnCl₆·Cl, (C₁₃H₁₅N₂)₄CuCl₁₀·4H₂O, and [(C₁₃H₁₆N₂)(C₂H₆NH₂)MnCl₄·2H₂O]·Cl. Our research delves into their fundamental optical properties and luminescence mechanisms, providing valuable insights for future studies.