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π-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(ii)/Au(iii) complex
Abstract
The synthesis and characterization of a mixed metal ruthenium(II)/gold(III) complex bridged by tetrapyridophenazine (tpphz) are described. It is isostructural and isoelectronic to the well-known photocatalysts with palladium(II) or platinum(II). Concentration dependent 1H-NMR spectroscopy and XRD studies show that the electrostatic repulsion between the gold(III) moieties exceeds the attractive π-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 π-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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Authors (8)
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Dieter Sorsche
- Ulm University Institute of Inorganic Chemistry
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Markus Schaub
- Ulm University Institute of Inorganic Chemistry
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Frank Heinemann
- Ulm University Institute of Inorganic and GeneralChemistry
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Johannes Habermehl
- Ulm University Institute of Inorganic Chemistry
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Susanne Kuhri
- IEK-3 Institute of Energy and Climate Research
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Dirk Guldi
- Fredrich Alexander Universitat Department Chemie and Pharmazie
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Sven Rau
- Ulm University Institute of Inorganic Chemistry
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Details
- Category:
- Articles
- Type:
- artykuł w czasopiśmie wyróżnionym w JCR
- Published in:
-
DALTON TRANSACTIONS
no. 45,
edition 32,
pages 12846 - 12853,
ISSN: 1477-9226 - Language:
- English
- Publication year:
- 2016
- Bibliographic description:
- Sorsche D., Schaub M., Heinemann F., Habermehl J., Kuhri S., Guldi D., Guthmuller J., Rau S.: π-Stacking attraction vs. electrostatic repulsion: competing supramolecular interactions in a tpphz-bridged Ru(ii)/Au(iii) complex// DALTON TRANSACTIONS. -Vol. 45, iss. 32 (2016), s.12846-12853
- DOI:
- Digital Object Identifier (open in new tab) 10.1039/c6dt01643j
- Verified by:
- Gdańsk University of Technology
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