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Luminescence in Functionalized Copper Thiolate Clusters – Synthesis and Structural Effects

Authors

  • Robert Langer,

    1. Institut für Anorganische Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany
    2. Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou 510275, China
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  • Munendra Yadav,

    1. Institut für Anorganische Chemie and DFG-Centrum für funktionelle Nanostrukturen (CFN), Karlsruher Institut für Technologie, Engesserstr. 15, 76133 Karlsruhe, Germany
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  • Bastian Weinert,

    1. Institut für Anorganische Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany
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  • Dieter Fenske,

    1. Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou 510275, China
    2. Institut für Anorganische Chemie and DFG-Centrum für funktionelle Nanostrukturen (CFN), Karlsruher Institut für Technologie, Engesserstr. 15, 76133 Karlsruhe, Germany
    3. Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany, http://www.int.kit.edu/
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  • Olaf Fuhr

    1. Lehn Institute of Functional Materials, Sun Yat-Sen University, Guangzhou 510275, China
    2. Institut für Anorganische Chemie and DFG-Centrum für funktionelle Nanostrukturen (CFN), Karlsruher Institut für Technologie, Engesserstr. 15, 76133 Karlsruhe, Germany
    3. Institut für Nanotechnologie, Karlsruher Institut für Technologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany, http://www.int.kit.edu/
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  • Dedicated to Professor Heinrich Nöth on the occasion of his 85th birthday

Abstract

A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 15 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu···Cu distances to cluster molecules with seven copper atoms and relatively short Cu···Cu distances, have been investigated. Compounds 15 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum (1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu···Cu distances (35), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups.

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