Photochemistry and Photophysics of Coordination Compounds

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194 S. Campagna et al. 1. To increase the absorption properties of the (multicomponent) sensitizer, by using systems featuring the antenna effect, with the energy trap of the antenna being the Ru(II) unit directly connected to the semiconductor. One example is the trinuclear Ru(II) species 71 showninFig.20;in71,the light absorbed by the peripheral Ru(II) chromophores is transferred quantitatively to the central Ru(II) chromophore, from which electron injection takes place [420]. Experiments on this complex adsorbed on polycrystalline TiO2 gave an overall conversion efficiency of ca. 7% withturnover numbers of at least 1 × 10 6 . The antenna effect is expected to be of relevance for applications requiring very thin TiO2 layers. 2. To spatially separate the injected electron and the hole on the sensitizer, so decreasing losses due to charge recombination. A system designed for this aim (72) is shown in Fig. 21, where the possible electron transfer steps are indicated [421]. In 72, the MLCT state of the Ru(II) unit is rapidly quenched by the Rh(III) species (step k1 in Fig. 21), followed by injection of the electron onto the semiconductor conductance band from the reduced Rh unit (step k2, in competition with step k4). The recombination process (k5) is slow because of a very weak electronic coupling. To reach thesameaim,thespecies73 shown in Fig. 22 has been designed [422]. Here, the first step is the electron injection from the Ru unit. Then, electron transfer from the phenothiazine unit to the oxidized Ru unit takes place, resulting in a charge-separated species which decays to the ground state with a rate of 3.6 × 10 3 s –1 (lifetime, 0.3 ms). The dyad and model molecules were also tested in solar cells, with iodide as an electron donor. While the observed IPCE was of the order of 45% for both systems, the open circuit photovoltage was higher for the dyad by 100 mV. The effect was more pronounced in the absence of iodide with Voc = 180 mV. Applying the measured interfacial electron transfer rates to the diode equation Fig. 20 Structural formula of a branched antenna system and schematization of energy transfer and charge injection in TiO2. Complex charge is omitted for clarity
Photochemistry and Photophysics of Coordination Compounds: Ruthenium 195 Fig. 21 Structural formula of a linear antenna system and schematization of energy transfer and charge injection in TiO2. Complex charge is omitted for clarity Fig. 22 Structural formula of TiO2/Ru-PTZ heterotriad system and schematization of the electron transfer steps. Complex charge is omitted for clarity
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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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