%0 Journal Article %T Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches %+ Institut des Sciences Chimiques de Rennes (ISCR) %+ Chifeng University %+ Durham University %+ Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM) %A Zhang, Xu %A Abid, Seifallah %A Shi, Limiao %A Williams, J. A. Gareth %A Fox, Mark A. %A Miomandre, Fabien %A Tourbillon, Clarisse %A Audibert, Jean-Frédéric %A Mongin, Olivier %A Paul, Frédéric %A Paul-Roth, Christine O. %Z CNRS %Z China Scholarship Council (CSC) %Z Ministere de l'Enseignement Superieur et de la Recherche Scientifique de Tunisie %< avec comité de lecture %@ 1477-9226 %J Dalton Transactions %I Royal Society of Chemistry %V 48 %N 31 %P 11897-11911 %8 2019-08-21 %D 2019 %R 10.1039/c9dt02087j %M 31310264 %K Porphyrin %K Fluorene %K Photoluminescence %K Ruthenium Alkynyl Complex %K Spectroelectrochemistry %Z Chemical SciencesJournal articles %X 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 %G English %2 https://univ-rennes.hal.science/hal-02278395/document %2 https://univ-rennes.hal.science/hal-02278395/file/CO%20Paul-Roth%20Dalton%20trans%202019.pdf %L hal-02278395 %U https://univ-rennes.hal.science/hal-02278395 %~ UNIV-RENNES1 %~ CNRS %~ ENS-CACHAN %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_OMC2012 %~ SCR_CPM %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ ISCR-CORINT %~ UR1-SDLM %~ UNIV-PARIS-SACLAY %~ ENS-CACHAN-SACLAY %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ ISCR-CORINT1 %~ TEST-HALCNRS %~ UR1-MMS %~ PPSM-AUTO %~ ENS-PARIS-SACLAY %~ ISCR-CORINT3 %~ GS-CHIMIE %~ GS-PHYSIQUE %~ TEST2-HALCNRS