Beyond Templating: Electronic Structure Impacts Of Aromatic Cations In Organic-Inorganic Antimony Chlorides

Organic 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)(4)Sb2Cl12 (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)(4)(SbSbCl12)-Sb-III-Cl-V 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.