Increasing the lifetimes of charge separated states in porphyrin–fullerene polyads
文献情報
Di Gao, Shawkat M. Aly, Paul-Ludovic Karsenti, Gessie Brisard, Pierre D. Harvey
Two linear polyads were designed using zinc(II)porphyrin, [ZnP], and N-methyl-2-phenyl-3,4-fullero-pyrrolidine (C60) where C60 is dangling either at the terminal position of [ZnP]–C6H4––C6H4–[ZnP]–C60 (1) or at the central position of [ZnP]–C6H4––C6H4–[ZnP(C60)]–C6H4––C6H4–[ZnP] (2) in order to test whether the fact of having one or two side electron donors influences the rate of electron transfer, ket. These polyads were studied using cyclic voltammograms, DFT computations, steady state and time-resolved fluorescence spectroscopy, and femtosecond transient absorption spectroscopy (fs-TAS). Photo-induced electron transfer confirmed by the detection of the charge separated state [ZnP˙+]/C60˙− from fs-TAS occurs with rates (ket) of 3–4 × 1010 s−1 whereas the charge recombinations (CRs) are found to produce the [ZnP] ground state via two pathways (central [ZnP˙+]/C60˙− (ps) and terminal central [ZnP˙+]/C60˙− (ns) producing [1ZnP] (ground state) and [3ZnP*]). The formation of the T1 species is more predominant for 2.
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