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Issue 30, 2014
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Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

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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.

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

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Publication details

The article was received on 11 Apr 2014, accepted on 16 Jun 2014 and first published on 16 Jun 2014


Article type: Paper
DOI: 10.1039/C4DT01034E
Citation: Dalton Trans., 2014,43, 11676-11686
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    Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

    M. G. Pfeffer, L. Zedler, S. Kupfer, M. Paul, M. Schwalbe, K. Peuntinger, D. M. Guldi, J. Guthmuller, J. Popp, S. Gräfe, B. Dietzek and S. Rau, Dalton Trans., 2014, 43, 11676
    DOI: 10.1039/C4DT01034E

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