Beyond templating: Electronic structure impacts of aromatic cations in organic–inorganic antimony chlorides

Abstract

AbstractOrganic cations influence the crystal packing and, less commonly, the electronic structure of hybrid organic–inorganic materials. Two new hybrid compounds prepared from solution, (PEA)SbCl6 and (PEA)4Sb2Cl12 (PEA=phenylethylammonium), demonstrate how the aromatic PEA cation modifies the crystal and electronic structures relative to inorganic antimony chlorides. In (PEA)SbCl6 the ethylammonium conformation results in a polar and chiral crystal structure, and the bandgap is characterized by organic‐inorganic charge transfer. In the mixed‐valence (PEA)4SbIIISbVCl12 the structure is a uniaxial elongation of that of inorganic analogs and the optoelectronic properties combine features of intervalence charge transfer and organic–inorganic charge transfer.