Stepwise sequential and parallel photoinduced charge separation in a porphyrin-triquinone tetrad

被引:29
作者
Springer, J [1 ]
Kodis, G [1 ]
de la Garza, L [1 ]
Moore, AL [1 ]
Moore, TA [1 ]
Gust, D [1 ]
机构
[1] Arizona State Univ, Ctr Study Early Events Photosynthesis, Dept Chem & Biochem, Tempe, AZ 85287 USA
关键词
D O I
10.1021/jp022424g
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A molecular tetrad consisting of a free base porphyrin (P) linked to a triquinone moiety consisting of a naphthoquinone bearing two benzoquinones (NQ-BQ(2)) has been synthesized and its photochemistry has been investigated using time-resolved spectroscopic techniques. Excitation of the porphyrin chromophore of the P-NQ-BQ(2) tetrad in benzonitrile solution is followed by photoinduced electron transfer with a rate constant of 8.3 x 10(10) s(-1) to produce an initial P.+-NQ(.-)-BQ(2) state with a quantum yield of unity. A charge shift reaction gives a final P.+-NQ-(BQ(.-)-BQ) charge-separated state, which decays to the ground state with a rate constant of 1.9 x 10(11) s(-1). The tetrad features both sequential and parallel multistep electron-transfer pathways. No evidence was found for significant involvement of direct electron transfer from the porphyrin first excited singlet state to a benzoquinone.
引用
收藏
页码:3567 / 3575
页数:9
相关论文
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