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Syntheses, Structures, and Comprehensive NMR Spectroscopic Investigations of Hetero-Chalcogenidometallates: The Right Mix toward Multinary Complexes

Authors

  • Eugen Ruzin Dr.,

    1. Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg (Germany), Fax: (+49) 6421 28 25751
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  • Eldar Zent Dipl.-Chem.,

    1. Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg (Germany), Fax: (+49) 6421 28 25751
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  • Eberhard Matern Dr.,

    1. Institut für Anorganische Chemie, Universität Karlsruhe (TH), Engesserstrasse 15, 76131 Karlsruhe (Germany)
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  • Werner Massa Prof. Dr.,

    1. Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg (Germany), Fax: (+49) 6421 28 25751
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  • Stefanie Dehnen Prof. Dr.

    1. Fachbereich Chemie, Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35043 Marburg (Germany), Fax: (+49) 6421 28 25751
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Abstract

Library of semiconductors: Mixtures of binary chalcogenidostannate anions in protic solution show statistic chalcogenide exchange (see scheme), which is examined by comprehensive NMR investigations, DFT calculations and chemical reactions. A simple approach is provided to generate a library of semiconductor compounds with finely tuned opto-electronic properties.

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Aqueous solutions of ternary ortho-chalcogenidostannate anions [SnE14−xE2x]4− (E1, E2=S, Se, Te) have been generated following different routes that all lead to equilibria of all possible permutations of binary and ternary anions. This has been rationalized by means of NMR studies that can be explained by calculations using density functional theory (DFT) methods. Thus, if one reacts such solutions with transition-metal ions, quaternary M/Sn/E1/E2 anions are obtained, which exhibit coordination by different ternary chalcogenidostannate ligands. The electronic excitation energies of the corresponding alkali metal salts lie between the Eg values of compounds containing either M/Sn/E1 or M/Sn/E2 anions. In this way, we provide a simple approach toward a library of semiconductor compounds with finely-tuned optoelectronic properties.

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