Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches - Université de Rennes Access content directly
Journal Articles Dalton Transactions Year : 2019

Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches

Abstract

Two dyads containing tris-and tetrakis-meso-fluorenyl-substituted porphyrin and ethynylruthenium units, 1 and 2, were investigated by emission spectro-electrochemical (SEC) methods for their potential use as fluorescence switches. The ruthenium group as a potential electron donor and the porphyrin as a potential electron acceptor are connected by a phenylene bridge in 1 and by a fluorenylene bridge in 2. The new fluorenyl-linked dyad 2 was probed by UV-visible, near-infrared (NIR) and infrared (IR) absorption SEC methods, and the properties interpreted with the aid of hybrid-DFT computations, for comparison with reported data for 1. The porphyrin-based fluorescence of 1 decreased in intensity upon oxidation to 1 + and decreased further on oxidising 1 + to 1 2+. Negligible change in the fluorescence intensity of 2 was observed upon oxidation to 2 + but the intensity decreased upon subsequent oxidation of 2 + to 2 2+. These findings contrast with data reported for some other porphyrins appended with redox-active ruthenium or iron units, where fluorescence intensities increase upon oxidation of the peripheral metal centers, but they match data reported more recently for closely related arrays. A rationale for these apparently contrasting observations is proposed. A c c e p t e d m a n u s c r i p t
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Dates and versions

hal-02278395 , version 1 (16-12-2019)

Identifiers

Cite

Xu Zhang, Seifallah Abid, Limiao Shi, J. A. Gareth Williams, Mark A. Fox, et al.. Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches. Dalton Transactions, 2019, 48 (31), pp.11897-11911. ⟨10.1039/c9dt02087j⟩. ⟨hal-02278395⟩
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