Photochemistry and Photophysics of Coordination Compounds

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32 V. Balzani et al. Fig. 19 Schematic representation of the operation of rotaxane D 6+ as a four-stroke linear nanomotor powered by sunlight [94] (c) Electronic reset: a back electron-transfer process from the “free” reduced station A – 1 to P+ (step 6) restores the electron-acceptor power to the A1 station. (d) Nuclear reset: as a consequence of the electronic reset, back movement of the ring from A2 to A1 takes place (step 7). The crucial point is the competion between ring displacement (step 4) and back electron transfer (step 5). The results revealed that in acetonitrile solution at room temperature the ring shuttling rate is one order of magnitude slower than the back electron transfer. Hence, the absorption of light can cause the occurrence of a forward and back ring movement (i.e., afullcycle)witha2% quantum yield. The low efficiency is compensated by the following features: (1) the operation of the system relies exclusively on intramolecular processes, without generation of any waste product; and (2) since [Ru(bpy)3] 2+ shows an intense absorption band in the visible region, the system works simply upon exposure to sunlight. A much higher efficiency
Photochemistry and Photophysics of Coordination Compounds 33 can be obtained by using an electron relay, again consuming only sunlight without generation of waste products [95]. 6 Conclusions Research on the photochemistry and photophysics of coordination compounds has shown an extraordinary quantitative development as well as profound qualitative changes over the years. Studies on intramolecular photoreactions and luminescence properties of coordination compounds of simple ligands have been followed by investigations on compounds containing complex synthetic ligands. Characterization of excited-state properties has been followed by extensive use of metal complexes in bimolecular processes. With the advent of supramolecular chemistry, luminescent and/or photoredox reactive metal complexes have been used as essential components in a bottomup approach to the construction of molecular devices and machines. In the next few years research on the photochemistry and photophysics of coordination compounds will largely be concentrated on the development of supramolecular systems for solar energy conversion and information processes. In this regard, it should be noted that the photoactive components presently used are very limited in number. Therefore, there is a need to extend basic research in order to discover novel mononuclear coordination compounds capable of exhibiting long excited-state lifetimes, reversible redox behavior, and stability toward photodecomposition. The large number of metals that can be used and the endless number of ligands that can be designed and synthesized open an ample horizon to these studies, as illustrated in the other chapters in this volume. Acknowledgements We acknowledge MIUR (PRIN projects no. 2006034123 & 2006030320), the University of Bologna and the University of Messina for financial support. References 1. John DHD, Field GTJ (1963) A textbook of photographic chemistry. Chapman and Hall, London 2. Balzani V, Carassiti V (1970) Photochemistry of coordination compounds. Academic, London 3. Ciamician G (1912) Science 36:385 4. Leighton WG, Forbes GS (1930) J Am Chem Soc 52:3139 5. Basolo F, Pearson RG (1958) Mechanisms of inorganic reactions. Wiley, New York 6. Ballhausen CJ (1962) Introduction to ligand field theory. McGraw-Hill, New York 7. Orgel LE (1954) Q Rev London 8:422 8. Jorgensen CK (1962) Absorption spectra and chemical bonding in complexes. Pergamon, Oxford
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