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Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(i) chromophore and a fullerene electron acceptor unit

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Abstract

A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties–including pump–probe transient absorption spectroscopy in the visible and near-infrared region–have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer (3MLLCT) state of the dinuclear rhenium(i) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

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Authors and Affiliations

  1. Dipartimento di Scienze Chimiche, Università di Messina and Centro Interuniversitario per la Conversione Chimica dell’Energia Solare (SOLAR-CHEM; sezione di Messina), Messina, Italy

    Francesco Nastasi, Fausto Puntoriero & Sebastiano Campagna

  2. Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara and Centro Interuniversitario per la Conversione Chimica dell’Energia Solare (SOLAR-CHEM; sezione di Ferrara), Ferrara, Italy

    Mirco Natali

  3. Dipartimento di Scienze Chimiche, Università di Padova, Padova, Italy

    Miriam Mba & Michele Maggini

  4. Dipartimento di Chimica, Università degli Studi di Milano, Milano, Italy

    Patrizia Mussini & Monica Panigati

  5. Istituto per lo Studio delle Macromolecole (ISMAC)-CNR, Milano, Italy

    Monica Panigati

  6. Istituto per la Sintesi Organica e la Fotoreattività (ISOF)-CNR, Bologna, Italy

    Sebastiano Campagna

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  1. Francesco Nastasi
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  2. Fausto Puntoriero
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  3. Mirco Natali
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  4. Miriam Mba
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  5. Michele Maggini
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  6. Patrizia Mussini
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  7. Monica Panigati
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  8. Sebastiano Campagna
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Additional information

Electronic supplementary information (ESI) available: General procedures, equipments and methods; synthesis and characterization details; ns flash photolysis of 1 and 2; near-infrared fs transient spectrum of 2; global kinetic analysis of 1, comments on the possible presence of diastereoisomers in 1, spectroelectrochemistry of 3. See DOI: 10.1039/c4pp00301b

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Nastasi, F., Puntoriero, F., Natali, M. et al. Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(i) chromophore and a fullerene electron acceptor unit. Photochem Photobiol Sci 14, 909–918 (2015). https://doi.org/10.1039/c4pp00301b

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