Molecular Decomposition Routes of Diaryl Diselenide Precursors in Relation to the Phase Determination of Copper Selenides

Alexandra C Koziel; Ralston B Goldfarb; Emma J Endres; Janet E Macdonald

doi:10.1021/acs.inorgchem.2c02042

Molecular Decomposition Routes of Diaryl Diselenide Precursors in Relation to the Phase Determination of Copper Selenides

Inorg Chem. 2022 Sep 19;61(37):14673-14683. doi: 10.1021/acs.inorgchem.2c02042. Epub 2022 Sep 7.

Authors

Alexandra C Koziel^{1

2}, Ralston B Goldfarb¹, Emma J Endres^{1

2}, Janet E Macdonald^{1

2}

Affiliations

¹ Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
² Vanderbilt Institute for Nanoscale Science and Engineering, Nashville, Tennessee 37235, United States.

PMID: 36069603
DOI: 10.1021/acs.inorgchem.2c02042

Abstract

¹H nuclear magnetic resonance (NMR), ⁷⁷Se NMR, and powder X-ray diffraction (XRD) were used to monitor the thermal decomposition of diphenyl and dibenzyl diselenide precursors toward the synthesis of copper selenides. Copper was found to promote the decomposition of both precursors. The inorganic nanocrystals and organic byproducts were sensitive to the specific diaryl diselenides and the presence of oleylamine and copper. Molecular mechanistic routes are proposed. Berzelianite (Cu_1.8Se), klockmannite (CuSe), umangite (Cu₃Se₂), and both petřı́čekite (m-CuSe₂) and krutaite (p-CuSe₂) were identified as products. Multistep transformations between phases were discovered through reactions with the organoselenium precursors, and organic decomposition products are proposed.