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Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

Abstract

The synthesis and characterisation of an asymmetric potential bridging ligand bmptpphz (bmptpphz = 2,17-bis(4-methoxyphenyl)tetrapyrido[3,2-a:2’,3’-c:3’’,2’’-h:2’’’,3’’’-j] phenazine) is presented. This ligand contains a 1,10-phenanthroline (phen) and a 2,9-disubstituted phen sphere and possesses a strong absorbance in the visible. Facile coordination of the phen sphere to a Ru(tbbpy)2 core leads to Ru(bmptpphz) ([(tbbpy)2Ru(bmptpphz)](PF6)2; tbbpy = 4,4’-di-tert-butyl-2,2’-bipyridine). UV-vis, emission, resonance Raman and theoretical investigations show that this complex possesses all properties associated with a Ru(tpphz) ([(tbbpy)2Ru(tpphz)](PF6)2; tpphz = tetrapyrido[3,2-a:2’,3’-c:3’’,2’’-h:2’’’,3’’’-j] phenazine) moiety and that the ligand based absorbances in the vis-part also populate an MLCT like state. The coordination of a Pd-core in the new 2,9-disubstituted phen sphere is possible, leading to a cyclometallation. The tridentate complexation leads to changes in the UV-vis and emission behaviour. Furthermore, the stability of the Pd-coordination is significantly enhanced if compared to the unsubstituted Ru(tpphz). Ru(bmptpphz)PdCl proved to be an active photocatalyst for H2 evolution, albeit with lower activity than the mother compound Ru(tpphz)PdCl2.

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Authors (12)

  • Photo of  M. Pfeffer

    M. Pfeffer

    • University of Ulm Institute of Inorganic Chemistry Materials and Catalysis
  • Photo of  L. Zedler

    L. Zedler

    • University in Jena Institute of Physical Chemistry
  • Photo of  S. Kupfer

    S. Kupfer

    • University in Jena Institute of Physical Chemistry
  • Photo of  M. Paul

    M. Paul

    • University in Jena Institute of Physical Chemistry
  • Photo of  M. Schwalbe

    M. Schwalbe

    • Berlin Univestitat Department of Chemistry
  • Photo of  K. Peuntinger

    K. Peuntinger

    • Berlin Universytat Department of Chemistry and Pharmacy and Interdyscyplinary Center for Molecular Materials
  • Photo of  D. Guldi

    D. Guldi

    • Berlin Universytat Department of Chemistry and Pharmacy and Interdyscyplinary Center for Molecular Materials
  • Photo of  J. Popp

    J. Popp

    • Universyty Jena Institute of Physical Chemistry and Abbe Center of Photonics
  • Photo of  S. Gräfe

    S. Gräfe

    • Universyty Jena Institute of Physical Chemistry and Abbe Center of Photonics
  • Photo of  B. Dietzek

    B. Dietzek

    • Universyty Jena Institute of Physical Chemistry and Abbe Center of Photonics
  • Photo of  S. Rau

    S. Rau

    • University of Ulm Institute of Inorganic Chemistry Materials and Catalysis

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Details

Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
DALTON TRANSACTIONS no. 43, edition 30, pages 76 - 86,
ISSN: 1477-9226
Language:
English
Publication year:
2014
Bibliographic description:
Pfeffer M., Zedler L., Kupfer S., Paul M., Schwalbe M., Peuntinger K., Guldi D., Guthmuller J., Popp J., Gräfe S., Dietzek B., Rau S.: Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium// DALTON TRANSACTIONS. -Vol. 43, iss. 30 (2014), s.76-86
DOI:
Digital Object Identifier (open in new tab) 10.1039/c4dt01034e
Verified by:
Gdańsk University of Technology

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