Accessing One-Dimensional Chains of Halogenoindates(III) in Organic-Inorganic Hybrids.

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX, InX, InX, or InX. Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here we report for the first time In-based organic-inorganic hybrids, (CHNS)InCl and (CHNS)InBr, with 1D anionic chains of -halide-bridged InX octahedra whose formation is guided by 2-mercaptopyrimidinium cations (CHNS). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In ions. The materials show a robust band gap predominantly governed by CHNS cations. Dielectric relaxation processes in (CHNS)InBr arise from the cations' dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In-based hybrids.