Two Pseudopolymorphic Star-Shaped Tetranuclear Co(3+) Compounds with Disulfide Anions Exhibiting Two Different Connection Modes and Promising Photocatalytic Properties.
Chemistry
; 21(39): 13637-45, 2015 Sep 21.
Article
em En
| MEDLINE
| ID: mdl-26270388
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]â
4 H2O (II) were obtained under solvothermal conditions (C6H14N2=trans-1,2-diaminocyclohexane). The structures feature S2(2-) ions exhibiting two different coordination modes. Terminal S2(2-) entities join two Co(3+) centres in a µ2 fashion, whereas the central S2(2-) groups connect four Co(3+) 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 Sâ
â
â
H bonding close contacts are associated with relatively weak Hâ
â
â
H interactions. A detailed DFT analysis of the bonding situation explains the long S-S bonds in the µ4-bridging S2(2-) units and the short bonds for the S2(2-) moieties in the µ2-connecting mode. Photocatalytic hydrogen evolution experiments demonstrate the potential of compound II as catalyst.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2015
Tipo de documento:
Article