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Dual Character of Excited Radical Anions in Aromatic Diimide Bis(radical anion)s: Donor or Acceptor?
journal contribution
posted on 2017-02-07, 00:00 authored by Chao Lu, Mamoru Fujitsuka, Akira Sugimoto, Tetsuro MajimaIntramolecular electron
transfer (ET) processes in the excited aromatic diimide bis(radical
anion)s (ADI•–*–ADI′•–) were systematically investigated by applying femtosecond laser
flash photolysis to bis(radical anion)s of naphthalenediimide (NDI)
and perylenediimide (PDI), including NDI•––m-NDI•–, NDI•––p-NDI•–, PDI•––m-PDI•–, and NDI•––m-PDI•– (m and p indicate the substitution positions). The excitation of
NDI•––m-NDI•– and NDI•––p-NDI•– initiated disproportionation reactions generating
NDI and NDI2– with different ET rate constants.
For the first time, the dual characteristics of ADI•–* were confirmed upon selective excitation of NDI•––m-PDI•–: NDI•–* was unambiguously demonstrated to function
as an electron donor in NDI•–*–m-PDI•–, whereas PDI•–* acted as an electron acceptor in NDI•––m-PDI•–* because
of the energetically preferable production of NDI–m-PDI2–. The relationship between the ET rate constants
and driving forces in ADI•–*–ADI′•– can be reasonably analyzed by using the Marcus
theory. The current findings provide a new viewpoint regarding the
bipolaron-generating nature of ADI•–*–ADI′•– and facilitate simulating various types of
photocarrier migration in the densely charged regions of homo- and
heterogeneous n-type semiconductor materials upon irradiation.
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Intramolecular electron transferphotocarrier migrationelectron donorelectron acceptorET rate constantssubstitution positionsMarcus theoryn-type semiconductor materialsPDIADINDIdisproportionation reactionsExcited Radical Anionsbipolaron-generating natureDual Characterfemtosecond laser flash photolysis
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