Redox-assisted ring closing reaction of the photogenerated cyclophanediene form of bis(ferrocenyl)dimethyldihydropyrene with interferrocene electronic communication switching.
Redox-assisted ring closing reaction of the photogenerated cyclophanediene form of bis(ferrocenyl)dimethyldihydropyrene with interferrocene electronic communication switching.
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DOI：
10.1021/ja8016494
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发表时间：
2008-05
影响因子：
15
通讯作者：
Satoshi Muratsugu;S. Kume;H. Nishihara
中科院分区：
文献类型：
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作者：
Satoshi Muratsugu;S. Kume;H. Nishihara
我们合成了二茂铁连接的二甲基二氢芘（DHP）衍生物并研究了它们的光化学和氧化还原行为。对于双(二茂铁乙炔基)二甲基二氢芘(1)，在可见光(578 nm)和紫外光(303 nm)交替照射下，闭合DHP形式(1c)和开放CPD形式(1o)之间发生可逆光异构化，产率较高，而双(五甲基二茂铁乙炔基)二甲基二氢芘(2)则没有发生光异构化。图1通过DHP部分的光异构化表现出二茂铁（Fc）部分之间电子通讯的可逆转换，并证明了由Fc部分氧化诱导的新型闭环反应。电子通讯的幅度 deltaE0'（两个 Fc 的氧化还原电位之间的差值）在 1c 中为 63 mV，在 1o 中为 16 mV，表明通过间隔基的电子通讯在 DHP 部分的更发达的 pi 共轭中得到增强。通过循环伏安图的模拟，估计从1o+到1c+和从1o2+到1c2+的闭环反应速率常数分别为3.7和0.50 s(-1)。
We synthesized ferrocene-attached dimethyldihydropyrene (DHP) derivatives and investigated their photochemical and redox behaviors. For bis(ferrocenylethynyl)dimethyldihydropyrene (1), reversible photoisomerization between the closed DHP form (1c) and the open CPD form (1o) occurred in high yields upon alternate irradiation of visible (578 nm) light and UV (303 nm) light, whereas no photoisomerization proceeded for bis(pentamethylferrocenylethynyl)dimethyldihydropyrene (2). 1 exhibited reversible switching of electronic communication between the ferrocene (Fc) moieties by photoisomerization of the DHP moiety and demonstrated a novel ring closing reaction induced by oxidation of the Fc moieties. The magnitude of electronic communication, deltaE0' (the difference between the redox potentials of two Fc's), was 63 mV in 1c and 16 mV in 1o, indicating that the electronic communication through the spacer is enhanced in the more developed pi-conjugation of the DHP moiety. The rate constants of the ring closing reaction from 1o+ to 1c+ and from 1o2+ to 1c2+ were estimated at 3.7 and 0.50 s(-1), respectively, by the simulation of cyclic voltammograms.