The Role of Connectivity on Electronic Properties of Lead Iodide Perovskite-Derived Compounds

[Image: see text] We use a layered solution crystal growth method to synthesize high-quality single crystals of two different benzylammonium lead iodide perovskite-like organic/inorganic hybrids. The well-known (C(6)H(5)CH(2)NH(3))(2)PbI(4) phase is obtained in the form of bright orange platelets, with a structure comprised of single ⟨100⟩-terminated sheets of corner-sharing PbI(6) octahedra separated by bilayers of the organic cations. The presence of water during synthesis leads to formation of a novel minority phase that crystallizes in the form of nearly transparent, light yellow bar-shaped crystals. This phase adopts the monoclinic space group P2(1)/n and incorporates water molecules, with structural formula (C(6)H(5)CH(2)NH(3))(4)Pb(5)I(14)·2H(2)O. The crystal structure consists of ribbons of edge-sharing PbI(6) octahedra separated by the organic cations. Density functional theory calculations including spin–orbit coupling show that these edge-sharing PbI(6) octahedra cause the band gap to increase with respect to corner-sharing PbI(6) octahedra in (C(6)H(5)CH(2)NH(3))(2)PbI(4). To gain systematic insight, we model the effect of the connectivity of PbI(6) octahedra on the band gap in idealized lead iodide perovskite-derived compounds. We find that increasing the connectivity from corner-, via edge-, to face-sharing causes a significant increase in the band gap. This provides a new mechanism to tailor the optical properties in organic/inorganic hybrid compounds.