Angewandte Chemie, Accepted Article.

Replacing the Pb–X octahedral building unit of A I PbX 3 perovskites (X = halide) with a pair of edge‐sharing Pb–X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report eight members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrizinium‐based cations with low‐lying π* orbitals that form the conduction band, substantially decreasing the expanded lattice’s bandgap. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with A II = pyridinium and ammonium, we can isolate the contributions of the pyrazinium‐based orbitals in the bandgap transition of A II Pb 2 X 6 . The organic‐molecule‐based conduction band and the inorganic‐ion‐based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.