Annulation of Tetrathiafulvalene to the Bay Region of Perylenediimide: Fast Electron-Transfer Processes in Polar and Nonpolar Solvents

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• 作者：Mohamed E. El-Khouly ; Michael Jaggi ; Belinda Schmid ; Carmen Blum ; Shi-Xia Liu ; Silvio Decurtins ; Kei Ohkubo ; Shunichi Fukuzumi
• 刊名：Journal of Physical Chemistry C
• 出版年：2011
• 出版时间：April 28, 2011
• 年：2011
• 卷：115
• 期：16
• 页码：8325-8334
• 全文大小：1197K
• 年卷期：v.115,no.16(April 28, 2011)
• ISSN：1932-7455

文摘

A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended 蟺-conjugated molecular dyad (TTF鈭扨DI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N鈥?/i>-bis(1-octylnonyl)benzoperylene-1鈥?2鈥?3,4:9,10-hexacarboxylic-1鈥?2鈥?anhydride-3,4:9,10-bis(imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF鈭扨DI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the light-induced process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, 蟺-conjugated TTF鈭扨DI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of TTF-diamine/Ph-PDI has been observed via the triplet excited PDI for the first time.