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Issue 6, 2010
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Substitution-controlled ultrafast excited-state processes in Ru–dppz-derivatives

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Ru–dppz (dppz = dipyrido[3,2-a:2′,3,3′-c]phenazine) complexes play an important role as environmentally sensitive luminescence sensors and building blocks for larger supramolecular compounds. Their photophysical properties are known to be highly sensitive to intermolecular solvent–solute interactions and solvent bulk-properties. Here, the synthesis and characterisation of a novel Ru–dppz derivative is reported. The potential of drastically tuning the photophysical properties of such complexes is exemplified, by introducing very simple structural modifications, namely bromine, into the dppz-ligand scaffold. The photophysics i.e. nature of excited states and the excited-state relaxation pathway of the various complexes has been investigated by means of electrochemical measurements, steady-state emission experiments and femtosecond time-resolved spectroscopy. It could be shown that the location of bromine substitution influences the relative energy between a luminescent and a non-luminescent metal-to-ligand charge-transfer state and therefore quenches or facilitates transitions between both. Hence it is illustrated that the luminescent properties and the underlying ultrafast excited-state dynamics of the complexes can be controlled by structural variations, i.e. by intramolecular interactions as opposed to changes in the intermolecular interactions.

Graphical abstract: Substitution-controlled ultrafast excited-state processes in Ru–dppz-derivatives

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The article was received on 31 Jul 2009, accepted on 13 Nov 2009 and first published on 16 Dec 2009

Article type: Paper
DOI: 10.1039/B915770K
Citation: Phys. Chem. Chem. Phys., 2010,12, 1357-1368

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    Substitution-controlled ultrafast excited-state processes in Ru–dppz-derivatives

    C. Kuhnt, M. Karnahl, S. Tschierlei, K. Griebenow, M. Schmitt, B. Schäfer, S. Krieck, H. Görls, S. Rau, B. Dietzek and J. Popp, Phys. Chem. Chem. Phys., 2010, 12, 1357
    DOI: 10.1039/B915770K

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