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Controllable Electronic Structures and Photoinduced Processes of Bay-Linked Perylenediimide Dimers and a Ferrocene-Linked Triad

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Details

Original languageEnglish
Pages (from-to)9631-9641
JournalChemistry: A European Journal
Volume22
Issue number28
DOIs
Publication statusPublished - 2016
Publication typeA1 Journal article-refereed

Abstract

A series of perylene-3,4,9,10-bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)2 is much larger than those of para- and meta-phenylene-bridged PDI dimers p-(PDI)2 and m-(PDI)2. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2-methyl-THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red-shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600nm to the near-IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time-resolved measurements on ferrocene-linked p-(PDI)2 revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron-transfer process in toluene.

ASJC Scopus subject areas

Keywords

  • Electron transfer, Electronic structure, Excimers, Perylenediimides, Photophysics

Publication forum classification

Field of science, Statistics Finland