Photochemistry and Photophysics of Coordination Compounds
Photochemistry and Photophysics of Coordination Compounds
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