Photochemistry and Photophysics of Coordination Compounds

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154 S. Campagna et al. Ru(II) racks based on different molecular strands (30, 31) havealsobeen recently studied [240] (S Campagna, unpublished results). The pyrimidinecontaining Ru complex exhibits a 3 MLCT emission with maximum at 758 nm
Photochemistry and Photophysics of Coordination Compounds: Ruthenium 155 in acetonitrile at room temperature (τ = 30 ns), which moves to 740 nm in nitrile glass at 77 K(τ = 335 ns) [240]. The pyrazine-containing species exhibits very similar emission properties (room temperature, acetonitrile: λmax = 765 nm; τ = 60 ns; 77 K, nitrile glass: 750 nm; τ = 400 ns) (S Campagna, unpublished results). For these species, the lowest (emitting) MLCT state(s) involve(s) the bridging ligands, as for the former rack-type complex discussed above. 5.2.2 Dendrimers Luminescent Ru(II) dendrimers have been deeply investigated and the field has been reviewed recently [2, 241–245]. We will only mention some examples. 5.2.2.1 Dendrimers Containing Only One Metal Center Unit The ruthenium compound 32 is a classical example of a dendrimer containing a luminescent ruthenium complex core surrounded by organic wedges. In this dendrimer, the 2,2 ′ -bipyridine (bpy) ligands of the {Ru(bpy)3} 2+ -type core carry branches containing 1,3-dimethoxybenzene- and 2-naphthyl-type chromophoric units [246]. All three types of chromophoric groups present in the dendrimer, namely, {Ru(bpy)3} 2+ , dimethoxybenzene, and naphthalene, are potentially luminescent species. In 32, however, the fluorescence of the dimethoxybenzene- and naphthyl-type units is almost completely quenched in acetonitrile solution, with concomitant sensitization of the {Ru(bpy)3} 2+ core luminescence. These results show that very efficient energy transfer processes take place, converting the very short-lived (nanosecond timescale) UV fluorescence of the aromatic units of the wedges to the relatively long-lived (microsecond timescale) orange luminescence of the metal-based dendritic core. This dendrimer is therefore an excellent example of a light-harvesting antenna system as well as of a species capable of acting as a frequency converter. It should also be noted that in aerated solution the phosphorescence intensity of the dendritic core is more than twice as intense as that of the
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280 Topics in Current Chemistry Edi
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Photochemistry and Photophysics of
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Volume Editors Prof. Vincenzo Balza
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Topics in Current Chemistry Also Av
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X Preface nation Compounds. The ven
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Contents Photochemistry and Photoph
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258 Author Index Volumes 251-280 Be
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Subject Index Alkyne bridges 148 An
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Subject Index 273 Rh(III) cyclometa
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