Tolerance Factor for Stabilizing 3D Hybrid Halide Perovskitoids Using Linear Diammonium Cations

Xiaotong Li, Mikaël Kepenekian, Linda Li, Hao Dong, Constantinos C. Stoumpos, Ram Seshadri, Claudine Katan, Peijun Guo, Jacky Even, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


Three-dimensional (3D) halide perovskites have attracted enormous research interest, but the choice of the A-site cations is limited by the Goldschmidt tolerance factor. In order to accommodate cations that lie outside the acceptable range of the tolerance factor, low-dimensional structures usually form. To maintain the favorable 3D connection, the links among the metal-halide octahedra need to be rearranged to fit the large cations. This can result in a departure from the proper corner-sharing perovskite architectures and lead to distinctly different perovskitoid motifs with edge- and face-sharing. In this work, we report four new 3D bromide perovskitoids incorporating linear organic diammonium cations, A′Pb2Br6 (A′ is a +2 cation). We propose a rule that can guide the further expansion of this class of compounds, analogous to the notion of Goldschmidt tolerance factor widely adopted for 3D AMX3 perovskites. The fundamental building blocks in A′Pb2Br6 consist of two edge-shared octahedra, which are then connected by corner-sharing to form a 3D network. Different compounds adopt different structural motifs, which can be transformed from one to another by symmetry operations. Electronic structure calculations suggest that they are direct bandgap semiconductors, with relatively large band dispersions created by octahedra connected by corner-sharing. They exhibit similar electronic band structures and dynamic lattice characteristics to the regular 3D AMX3 perovskites. Structures with smaller Pb-Br-Pb angles and larger octahedra distortion exhibit broad photoluminescence at room temperature. The emerging structure-property relationships in these 3D perovskitoids set the foundation for designing and investigating these compounds for a variety of optoelectronic applications.

Original languageEnglish (US)
Pages (from-to)3902-3912
Number of pages11
JournalJournal of the American Chemical Society
Issue number9
StatePublished - Mar 9 2022

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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