pi-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(II)/Au(III) complex

Sorsche Dieter; Schaub Markus; Heinemann Frank W.Habermehl JohannesKuhri SusanneGuldi DirkGuthmuller JulienRau Sven

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pi-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(II)/Au(III) complex

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The synthesis and characterization of a mixed metal ruthenium(II)/gold(III) complex bridged by tetrapyrido-phenazine (tpphz) are described. It is isostructural and isoelectronic to the well-known photocatalysts with palladium(II) or platinum(II). Concentration dependent H-1-NMR spectroscopy and XRD studies show that the electrostatic repulsion between the gold(III) moieties exceeds the attractive p-stacking interaction. Theoretical calculations based on the new structural data confirm an increased positive charge on the bridging ligand as well as significantly altered orbital symmetry as compared to the previously investigated palladium(II) complex. This is the first example of a tpphz ruthenium(II) complex where p-stacking is completely inhibited. The detailed investigation of the solid-state structure showed for the first time in bimetallic tpphz bridged complexes no significant torsion within the bridging ligand itself. Although catalytic performance for proton reduction by gold(III) is naturally not observed, its photochemical decomposition in colloidal gold particles could be shown by TEM and DLS.

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《Dalton transactions: An international journal of inorganic chemistry》 |2016年第32期|12846-12853|共8页
作者
Sorsche Dieter; Schaub Markus; Heinemann Frank W.Habermehl JohannesKuhri SusanneGuldi DirkGuthmuller JulienRau Sven;
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Univ Ulm, Inst Inorgan Chem 1, Albert Einstein Allee 11, D-89081 Ulm, Germany;

Inst Inorgan & Gen Chem, Egerlandstr 1, D-91058 Erlangen, Germany;

Univ Erlangen Nurnberg, Dept Chem & Pharm, Lehrstuhl Phys Chem 1, Egerlandstr 3, D-91058 Erlangen, GermanyGdansk Univ Technol, Fac Appl Phys & Math, Narutowicza 11-12, PL-80233 Gdansk, PolandElect Proc Engn IEK 3, Inst Energy & Climate Res, Wilhelm Johnen Str, D-52428 Julich, Germany;

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正文语种英语
中图分类化学;无机化学;
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pi-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(II)/Au(III) complex

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