Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites

Daiki Umeyama, Linn Leppert, Bridget A. Connor, Mary Anne Manumpil, Jeffrey B. Neaton, Hemamala I. Karunadasa*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

18 Citations (Scopus)


Replacing the Pb−X octahedral building unit of AIPbX3 perovskites (X=halide) with a pair of edge-sharing Pb−X octahedra affords the expanded perovskite analogs: AIIPb2X6. We report seven 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 pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of AIIPb2X6. 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.

Original languageEnglish
Pages (from-to)19087-19094
Number of pages8
JournalAngewandte Chemie - International Edition
Issue number43
Publication statusPublished - 19 Oct 2020
Externally publishedYes


  • 3D halide perovskite analogs
  • charge separation
  • lattice expansion
  • radical doping


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