Photochemistry and Photophysics of Coordination Compounds

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196 S. Campagna et al. gave the predicted increase of Voc of 200 mV, which was in agreement with the obtained value (180 mV) [422]. It is interesting that an increase of the lifetime of the interfacial charge-separated state TiO2(e – )–Ru(II)– PTZ + has a direct influence on the overall efficiency of the cell. A similar approach inspired the design of the supramolecular species 74, basedon the “red dye” N3 sensitizer. Optical excitation of a nanocrystalline TiO2 film dye coated with such a species showed a long-lived charge-separated state [423]. 8 Miscellanea The fields that have been recently powered by Ru photochemistry are much more than those reported in some detail in this article. A few of those that are not discussed above will be briefly mentioned. Ru(II)-based chromophores have been linked to a plethora of receptor species, like calixarenes, crowns, and azacrowns, essentially for sensing purposes [280, 424, 425]. Ru(II) chromophores have also been embedded in oxygen-permeating polymers to yield luminescent sensors for molecular oxygen determination in atmosphere [426–429]. New systems have been designed and studied for obtaining OLED materials. In this regard, a dinuclear Ru complex has been used in conjunction with an organic luminophore to generate two-color electroluminescence [430]. Multichromophoric species made of Ru(II) chromophores interfaced with organic aromatics having suitable triplet-state levels have been studied to extend the lifetime of the MLCT excited state by a sort of delayed luminescence involving intercomponent energy transfer, with the organic triplet states used as excited-state energy storage systems [431–440, 442]. A few such species are compounds 75 (which is the first reported example of such a behavior [431]), 76 [437], and 77 [435]. Compound 77 is one of the species featuring the most outstanding behavior: its emission in fluid solution at room temperature (with maximum at about 600 nm) has lifetimes ranging from 43 µs (acetone solution) to 61 µs (acetonitrile)to115 µs (DMSO solution) [435]. With the aim of increasing the excited-state lifetime as well as the luminescence
Photochemistry and Photophysics of Coordination Compounds: Ruthenium 197 quantum yield, a goal which is missed by the formerly mentioned multichromophoric species, several Ru(II) chromophores having polypyridine ligands able to feature extended electron delocalization in their structure have been prepared [441]. In this case, the improved photophysical properties are due to reduced Franck–Condon factors for radiationless decay, a consequence of extended delocalization of the emitting MLCT state [78, 157, 443–446]. A typical example is the compound 78 shown in Fig. 23 [445]. In 78, in spite of the quite low emission energy at room temperature (820 nm), a relatively long luminescence lifetime and high quantum yield are found (420 ns and about 0.01, respectively). Hydrogen-bonded or, generally, noncovalently linked supramolecular species exhibiting photoinduced electron and/or energy transfer have also been prepared to mimic natural systems (see, for example, 79–81) [447–452]. Efficient intercomponent energy transfer through the noncovalently linked frameworks is usually obtained. However, in some cases the interest in the potential application of these systems is reduced by the small value of the association constants.
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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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