Cs3Cu4In2Cl13 Nanocrystals: A Perovskite-Related Structure with Inorganic Clusters at A Sites

Roman Kaiukov, Guilherme Almeida, Sergio Marras, Zhiya Dang, Dmitry Baranov, Urko Petralanda, Ivan Infante, Enrico Mugnaioli, Andrea Griesi, Luca De Trizio, Mauro Gemmi, Liberato Manna*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

An effort to synthesize the Cu(I) variant of a lead-free double perovskite isostructural with Cs2AgInCl6 resulted in the formation of Cs3Cu4In2Cl13 nanocrystals with an unusual structure, as revealed by single-nanocrystal three-dimensional electron diffraction. These nanocrystals adopt a A2BX6 structure (K2PtCl6 type, termed vacancy ordered perovskite) with tetrahedrally coordinated Cu(I) ions. In the structure, 25% of the A sites are occupied by [Cu4Cl]3+ clusters (75% by Cs+), and the B sites are occupied by In3+. Such a Cs3Cu4In2Cl13 compound prepared at the nanoscale is not known in the bulk and is an example of a multinary metal halide with inorganic cluster cations residing in A sites. The stability of the compound was supported by density functional theory calculations that also revealed that its bandgap is direct but parity forbidden. The existence of the Cs3Cu4In2Cl13 structure demonstrates that small inorganic cluster cations can occupy A sites in multinary metal halides.

Original languageEnglish
Pages (from-to)548-554
Number of pages7
JournalInorganic Chemistry
Volume59
Issue number1
Early online date12 Dec 2019
DOIs
Publication statusPublished - 6 Jan 2020

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Kaiukov, R., Almeida, G., Marras, S., Dang, Z., Baranov, D., Petralanda, U., ... Manna, L. (2020). Cs3Cu4In2Cl13 Nanocrystals: A Perovskite-Related Structure with Inorganic Clusters at A Sites. Inorganic Chemistry, 59(1), 548-554. https://doi.org/10.1021/acs.inorgchem.9b02834