Surfactants as additives make the structures of organic-inorganic hybrid bromoplumbates diverse

Although surfactant-facilitated crystallization has been widely used in pharmaceuticals, metal-organic frameworks (MOFs), chalcogenides and colloidal nanocrystals, using surfactants as additives to control the crystal growth of metal halides in the macroscale is unexplored. In this contribution, we used N-methylate 4,4′-bipyridine bromoplumbates as a model system to prove that surfactants as additives could make the structures of organic-inorganic hybrid bromoplumbates diverse. By only changing different surfactants, four new hybrid bromoplumbates including the first novel 3D open framework hybrid bromoplumbate [(C₁₂N₂H₁₄)₂Pb₇Br₁₈] (except perovskites) and a pair of 1D polymorphs were obtained. The related physical properties including optical band gaps, FT-IR and TGA-DSC for the as-obtained compounds have been carefully investigated. In addition, an interesting mother-liquor-facilitated single-crystal-to-single-crystal (SCSC) phase transition is also revealed. Our strategy to employ surfactants to control the crystal growth of metal halides could offer exciting opportunities for discovering novel organic-inorganic hybrid crystals with diverse structures and distinctive properties.