Two Pseudopolymorphic Star‐Shaped Tetranuclear Co3+ Compounds with Disulfide Anions Exhibiting Two Different Connection Modes and Promising Photocatalytic Properties |
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| Authors: | Dr. Nicole Pienack Henning Lühmann John Djamil Stefan Permien Prof. Dr. Christian Näther Sebastian Haumann Dr. Richard Weihrich Prof. Dr. Wolfgang Bensch |
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| Affiliation: | 1. Institute of Inorganic Chemistry, Christian‐Albrechts‐University of Kiel, Max‐Eyth‐Strasse 2, 24118 Kiel (Germany);2. Institute of Inorganic Chemistry, University of Regensburg, Universit?tsstrasse 31, 93040 Regensburg (Germany) |
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| Abstract: | The compound [Co4(C6H14N2)4(μ4‐S2)2(μ2‐S2)4] ( I ) and the pseudo‐polymorph [Co4(C6H14N2)4(μ4‐S2)2(μ2‐S2)4] ? 4 H2O ( II ) were obtained under solvothermal conditions (C6H14N2=trans‐1,2‐diaminocyclohexane). The structures feature S22? ions exhibiting two different coordination modes. Terminal S22? entities join two Co3+ centres in a μ2 fashion, whereas the central S22? groups connect four Co3+ cations in a μ4‐ coordination mode. Compound II can be transformed into compound I by heat and storage over P2O5 and storing compound I in humid air yields in the formation of compound II . The intermolecular interactions investigated through Hirshfeld surface analysis reveal that besides S???H bonding close contacts are associated with relatively weak H???H interactions. A detailed DFT analysis of the bonding situation explains the long S?S bonds in the μ4‐bridging S22? units and the short bonds for the S22? moieties in the μ2‐connecting mode. Photocatalytic hydrogen evolution experiments demonstrate the potential of compound II as catalyst. |
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| Keywords: | cobalt density functional calculations disulfide bridges Hirshfeld surface photocatalysis |
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