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 language | English |
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Pages (from-to) | 548-554 |
Number of pages | 7 |
Journal | Inorganic Chemistry |
Volume | 59 |
Issue number | 1 |
Early online date | 12 Dec 2019 |
DOIs | |
Publication status | Published - 6 Jan 2020 |
Funding
The authors thank Anatolii Polovitsyn for his help in developing the synthesis, Mirko Prato for the XPS analysis, and Simone Lauciello for carrying out the SEM-EDS measurements. The authors also acknowledge funding from the programme for research and Innovation Horizon 2020 (2014–2020) under the Marie Skłodowska-Curie Grant Agreement COMPASS 691185. The work of D.B. was supported by the European Union’s Horizon 2020 research and innovation programme under Marie Sklodowska-Curie Grant 794560 (RETAIN). I.I. acknowledges the Dutch NWO for financial support under the Vidi scheme (Grant 723.013.002).
Funders | Funder number |
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Dutch NWO | 723.013.002 |
European Union’s Horizon 2020 | |
Horizon 2020 Framework Programme | 794560 |
Horizon 2020 | 2020, 691185 |
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CSD 1955351: Experimental Crystal Structure Determination
Kaiukov, R. (Contributor), Almeida, G. (Contributor), Marras, S. (Contributor), Dang, Z. (Contributor), Baranov, D. (Contributor), Petralanda, U. (Contributor), Infante, I. (Contributor), Mugnaioli, E. (Contributor), Griesi, A. (Contributor), De Trizio, L. (Contributor), Gemmi, M. (Contributor) & Manna, L. (Contributor), Unknown Publisher, 6 Jan 2020
DOI: 10.25505/fiz.icsd.cc23mpv9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc23mpv9&sid=DataCite
Dataset / Software: Dataset
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CSD 1955353: Experimental Crystal Structure Determination
Kaiukov, R. (Contributor), Almeida, G. (Contributor), Marras, S. (Contributor), Dang, Z. (Contributor), Baranov, D. (Contributor), Petralanda, U. (Contributor), Infante, I. (Contributor), Mugnaioli, E. (Contributor), Griesi, A. (Contributor), De Trizio, L. (Contributor), Gemmi, M. (Contributor) & Manna, L. (Contributor), Unknown Publisher, 1 Jan 2020
DOI: 10.25505/fiz.icsd.cc23mpxc, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc23mpxc&sid=DataCite
Dataset / Software: Dataset