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二芳基二硒醚前驱体的分子分解途径与硒化铜相测定的关系

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

作者信息

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

机构信息

Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.

Vanderbilt Institute for Nanoscale Science and Engineering, Nashville, Tennessee 37235, United States.

出版信息

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

Abstract

H nuclear magnetic resonance (NMR), Se 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 (CuSe), klockmannite (CuSe), umangite (CuSe), and both petřı́čekite (-CuSe) and krutaite (-CuSe) were identified as products. Multistep transformations between phases were discovered through reactions with the organoselenium precursors, and organic decomposition products are proposed.

摘要

利用氢核磁共振(NMR)、硒核磁共振和粉末X射线衍射(XRD)来监测二苯基二硒化物和二苄基二硒化物前驱体在合成硒化铜过程中的热分解。发现铜能促进这两种前驱体的分解。无机纳米晶体和有机副产物对特定的二芳基二硒化物以及油胺和铜的存在很敏感。提出了分子机理途径。确认产物包括贝齐里乌斯矿(CuSe)、克洛曼矿(CuSe)、乌曼石(CuSe)以及佩特里切克矿(-CuSe)和克鲁泰矿(-CuSe)。通过与有机硒前驱体的反应发现了相之间的多步转变,并提出了有机分解产物。

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