Issue 10, 2015

On–off switch of charge-separated states of pyridine-vinylene-linked porphyrin–C60 conjugates detected by EPR


The design, synthesis, and electronic properties of a new series of D–π–A conjugates consisting of free base (H2P) and zinc porphyrins (ZnP) as electron donors and a fullerene (C60) as electron acceptor, in which the two electroactive entities are covalently linked through pyridine-vinylene spacers of different lengths, are described. Electronic interactions in the ground state were characterized by electrochemical and absorption measurements, which were further supported with theoretical calculations. Most importantly, charge-transfer bands were observed in the absorption spectra, indicating a strong pushpull behavior. In the excited states, electronic interactions were detected by selective photoexcitation under steady-state conditions, by time-resolved fluorescence investigations, and by pump probe experiments on the femto-, pico-, and nanosecond time scales. Porphyrin fluorescence is quenched for the different D–π–A conjugates, from which we conclude that the deactivation mechanisms of the excited singlet states are based on photoinduced energy- and/or electron transfer processes between H2P/ZnP and C60, mediated through the molecular spacers. The fluorescence intensity decreases and the fluorescence lifetimes shorten as the spacer length decreases and as the spacer substitution changes. With the help of transient absorption spectroscopy, the formation of charge-separated states involving oxidized H2P/ZnP and reduced C60 was confirmed. Lifetimes of the corresponding charge-separated states, which ranged from ∼400 picoseconds to 165 nanoseconds, depend on the spacer length, the spacer substitution, and the solvent polarity. Interestingly, D–π–A conjugates containing the longest linkers did not necessarily exhibit the longest charge-separated state lifetimes. The distances between the electron donors and the acceptors were calculated by molecular modelling. The longest charge-separated state lifetime corresponded to the D–π–A conjugate with the longest electron donor–acceptor distance. Likewise, EPR measurements in frozen media revealed charge separated states in all the D–π–A conjugates investigated. A sharp peak with g values ∼2.000 was assigned to reduced C60, while a broader, less intense signal (g ∼ 2.003) was assigned to oxidized H2P/ZnP. On–off switching of the formation and decay of the charge-separated states was detected by EPR at 77 K by repeatedly turning the irradiation source on and off.

Graphical abstract: On–off switch of charge-separated states of pyridine-vinylene-linked porphyrin–C60 conjugates detected by EPR

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Article type
Edge Article
08 Jun 2015
09 Jul 2015
First published
09 Jul 2015
This article is Open Access

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Creative Commons BY license

Chem. Sci., 2015,6, 5994-6007

On–off switch of charge-separated states of pyridine-vinylene-linked porphyrin–C60 conjugates detected by EPR

S. V. Kirner, D. Arteaga, C. Henkel, J. T. Margraf, N. Alegret, K. Ohkubo, B. Insuasty, A. Ortiz, N. Martín, L. Echegoyen, S. Fukuzumi, T. Clark and D. M. Guldi, Chem. Sci., 2015, 6, 5994 DOI: 10.1039/C5SC02051D

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