Abstract
We report three new rhenium chalcohalide cluster compounds, Re6S8I2, Re6S4Se4I2, and Re6Se8I2. The materials crystallize in the three-dimensional (3D) Re6S8Cl2 structure type with the space group P21/n. They can be synthesized with sufficiently large iodine gas pressures or using alkali metal iodide salt fluxes with excess iodine. All three compounds are thermally stable under vacuum up to 1000 °C, and density functional theory (DFT) calculation results predict them to be direct-gap semiconductors. The measured work functions, which are the valence band maxima with respect to vacuum, and the measured band gaps are 5.49(5) and 1.69(5) eV, 5.24(5) and 1.54(5) eV, and 5.03(5) and 1.44(5) eV for Re6S8I2, Re6S4Se4I2, and Re6Se8I2, respectively. They exhibit red to near-IR photoluminescence ranging from 1.38 eV (898 nm) to 1.93 eV (642 nm) centered at 1.67 eV (742 nm) for Re6S8I2 and ranging from 1.35 eV (918 nm) to 1.70 eV (726 nm) centered at 1.49 eV (832 nm) for Re6Se8I2 with average lifetimes of 5.15 and 1.83 ns, respectively.
Original language | English (US) |
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Pages (from-to) | 5780-5789 |
Number of pages | 10 |
Journal | Chemistry of Materials |
Volume | 33 |
Issue number | 14 |
DOIs | |
State | Published - Jul 27 2021 |
Funding
This work was supported by the National Science Foundation through the MRSEC program (NSF-DMR-1720139) at the Materials Research Center (C.C.L.) and DMR-2003476 (D.G.C.). This work made use of the Ag-microsource diffractometer in the IMSERC X-RAY facility at Northwestern University to obtain results included in this publication, the purchase of which was supported by the Major Research Instrumentation Program from the National Science Foundation under award CHE-1920248. This work made use of the IMSERC PCM facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633) and Northwestern University. This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF-DMR-1720139). Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The authors would like to acknowledge Michael Quintero and Rebecca McClain for productive conversations.
ASJC Scopus subject areas
- General Chemistry
- General Chemical Engineering
- Materials Chemistry
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CSD 2083085: Experimental Crystal Structure Determination
Laing, C. C. (Contributor), Shen, J. (Contributor), Chica, D. G. (Contributor), Cuthriell, S. A. (Contributor), Schaller, R. D. (Contributor), Wolverton, C. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc27xm93, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc27xm93&sid=DataCite
Dataset
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CSD 2083084: Experimental Crystal Structure Determination
Laing, C. C. (Contributor), Shen, J. (Contributor), Chica, D. G. (Contributor), Cuthriell, S. A. (Contributor), Schaller, R. D. (Contributor), Wolverton, C. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc27xm82, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc27xm82&sid=DataCite
Dataset
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CSD 2083086: Experimental Crystal Structure Determination
Laing, C. C. (Contributor), Shen, J. (Contributor), Chica, D. G. (Contributor), Cuthriell, S. A. (Contributor), Schaller, R. D. (Contributor), Wolverton, C. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc27xmb4, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc27xmb4&sid=DataCite
Dataset