Pienack, Nicole, Luehmann, Henning, Djamil, John, Permien, Stefan, Naether, Christian, Haumann, Sebastian, Weihrich, Richard and Bensch, Wolfgang (2015) Two Pseudopolymorphic Star-Shaped Tetranuclear Co3+ Compounds with Disulfide Anions Exhibiting Two Different Connection Modes and Promising Photocatalytic Properties. Chemistry-a European Journal, 21 (39). pp. 13637-13645. DOI 10.1002/chem.201501796.

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Abstract

The compound [Co-4(C6H14N2)(4)((4)-S-2)(2)((2)-S-2)(4)] (I) and the pseudo-polymorph [Co-4(C6H14N2)(4)((4)-S-2)(2)((2)-S-2)(4)]4H(2)O (II) were obtained under solvothermal conditions (C6H14N2=trans-1,2-diaminocyclohexane). The structures feature S-2(2-) ions exhibiting two different coordination modes. Terminal S-2(2-) entities join two Co3+ centres in a (2) fashion, whereas the central S-2(2-) groups connect four Co3+ cations in a (4)- 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 SH bonding close contacts are associated with relatively weak HH interactions. A detailed DFT analysis of the bonding situation explains the long SS bonds in the (4)-bridging S-2(2-) units and the short bonds for the S-2(2-) moieties in the (2)-connecting mode. Photocatalytic hydrogen evolution experiments demonstrate the potential of compound II as catalyst.

Document Type:	Article
Additional Information:	Times Cited: 0
Keywords:	cobalt density functional calculations disulfide bridges Hirshfeld surface photocatalysis
Research affiliation:	Kiel University Kiel University > Kiel Marine Science OceanRep > The Future Ocean - Cluster of Excellence
Refereed:	Yes
Open Access Journal?:	No
Publisher:	Wiley
Projects:	Future Ocean
Date Deposited:	18 Oct 2016 03:47
Last Modified:	23 Sep 2019 23:54
URI:	https://oceanrep.geomar.de/id/eprint/32632

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