Polymeric Metal Halides with Bright Luminescence and Versatile Processability

Abstract Most of current metal halide materials, including all inorganic and organic–inorganic hybrids, are crystalline materials with poor workability and plasticity that limit their application scope. Here, we develop a novel class of materials termed polymeric metal halides (PMHs) through introducing polycations into antimony‐based metal halide materials as A‐site cations. A series of PMHs with orange‐yellow broadband emission and large Stokes shift originating from inorganic self‐trapped excitons are successfully prepared, which meanwhile exhibit the excellent processability and formability of polymers. The versatility of these PMHs is manifested as the broad choices of polycations, the ready extension to manganese‐ and copper‐based halides, and the tolerance to molar ratios between polycations and metal halides in the formation of PMHs. The merger of polymer chemistry and inorganic chemistry thus provides a novel generic platform for the development of metal halide functional materials.