Photonic switching of photoinduced electron transfer in a dihydropyrene-porphyrin-fullerene molecular triad

被引:100
作者
Liddell, PA
Kodis, G
Andréasson, J
de la Garza, L
Bandyopadhyay, S
Mitchell, RH
Moore, TA
Moore, AL
Gust, D
机构
[1] Univ Victoria, Dept Chem, Victoria, BC V8W 3V6, Canada
[2] Arizona State Univ, Dept Chem & Biochem, Ctr Study Early Events Photosynthesis, Tempe, AZ 85287 USA
关键词
D O I
10.1021/ja039800a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Photonic control of photoinduced electron transfer has been demonstrated in a dimethyldihydropyrene (DHP) porphyrin (P) fullerene (C-60) molecular triad. In the DHP-P-C-60 form of the triad, excitation of the porphyrin moiety is followed by photoinduced electron transfer to give a DHP-P.+-C-60(.-) charge-separated state, which evolves by a charge shift reaction to DHP.+-P-C-60(.-). This final state has a lifetime of 2 mus and is formed in an overall yield of 94%. Visible (greater than or equal to300 nm) irradiation of the triad leads to photoisomerization of the DHP moiety to the cyclophanediene (CPD). Excitation of the porphyrin moiety of CPD-P-C-60 produces a short-lived (<10 ns) CPD-P center dot+-C-60(.-) state, but charge shift to the CPD moiety does not occur, due to the relatively high oxidation potential of the CPD group. Long-lived charge separation is not observed. Irradiation of CPD-P-C-60 with UV (254 nm) light converts the triad back to the DHP form. Thermal interconversion of the DHP and CPD forms is very slow, photochemical cycling is facile, and in the absence of oxygen, many cycles may be performed without substantial degradation. Thus, light is used to switch long-lived photoinduced charge separation on or off. The principles demonstrated by the triad may be useful for the design of molecule-based optoelectronic systems.
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页码:4803 / 4811
页数:9
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