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Photochemistry and Photophysics of Coordination Compounds

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Top Curr Chem (2007) 280: 117–214<br />

DOI 10.1007/128_2007_133<br />

© Springer-Verlag Berlin Heidelberg<br />

Published online: 27 June 2007<br />

<strong>Photochemistry</strong> <strong>and</strong> <strong>Photophysics</strong><br />

<strong>of</strong> <strong>Coordination</strong> <strong>Compounds</strong>: Ruthenium<br />

Sebastiano Campagna 1 (✉)·FaustoPuntoriero 1 ·FrancescoNastasi 1 ·<br />

Giacomo Bergamini 2 · Vincenzo Balzani 2<br />

1Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica,<br />

Università di Messina, Via Sperone 31, 98166 Messina, Italy<br />

campagna@unime.it<br />

2Dipartimento di Chimica “G. Ciamician”, Università di Bologna, Via Selmi 2,<br />

40126 Bologna, Italy<br />

1 Introduction .................................. 118<br />

2 Structure, Bonding, <strong>and</strong> Excited States <strong>of</strong> Ru(II) Polypyridine Complexes 119<br />

3 [Ru(bpy)3] 2+ : The Prototype ......................... 123<br />

3.1 AbsorptionSpectrum ............................. 123<br />

3.2 Deactivation<strong>of</strong>UpperExcitedStates..................... 124<br />

3.3 EmissionProperties .............................. 124<br />

3.4 Photosubstitution<strong>and</strong>PhotoracemizationProcesses ............ 127<br />

3.5 Quenching <strong>of</strong> the 3 MLCT Excited State:<br />

Energy<strong>and</strong>ElectronTransferProcesses ................... 128<br />

3.6 Chemiluminescence<strong>and</strong>ElectrochemiluminescenceProcesses....... 131<br />

4 Some Important Features <strong>of</strong> Ru(II) Polypyridine Complexes ....... 133<br />

4.1 Nonradiative Decay Rate Constants <strong>and</strong> Emission Spectral Pr<strong>of</strong>iles<br />

<strong>of</strong>Ru(II)PolypyridineComplexes ...................... 133<br />

4.2 Ultrafast Time-Resolved Spectroscopy<br />

<strong>and</strong>Localization/DelocalizationIssues .................... 135<br />

4.3 Ru(II)ComplexesBasedonTridentatePolypyridineLig<strong>and</strong>s........ 136<br />

4.4 Interplay Between Multiple Low-Lying MLCT States<br />

InvolvingaSinglePolypyridineLig<strong>and</strong>.................... 138<br />

5 Ruthenium <strong>and</strong> Supramolecular <strong>Photochemistry</strong> .............. 141<br />

5.1 Photoinduced Electron/Energy Transfer Across Molecular Bridges<br />

inDinuclearMetalComplexes......................... 142<br />

5.2 Photoactive Multinuclear Ruthenium Species<br />

ExhibitingParticularTopologies ....................... 153<br />

5.2.1 Racks<strong>and</strong>Grids ................................ 153<br />

5.2.2 Dendrimers................................... 155<br />

5.3 Donor–Chromophore–AcceptorTriads.................... 164<br />

5.4 PolyadsBasedonOligoprolineAssemblies.................. 170<br />

5.5 Multi-ruthenium Assemblies Based on Derivatized Polystyrene . . . . . . 172<br />

5.6 Photoinduced Collection <strong>of</strong> Electrons<br />

intoaSingleSite<strong>of</strong>aMetalComplex..................... 174<br />

5.7 PhotoinducedMultiholeStorage:MixedRu–MnComplexes ........ 177<br />

5.8 PhotocatalyticProcessesOperatedbySupramolecularSpecies....... 180

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