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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Accès libre
    In- and Out-of-Cavity Interactions by Modulating the Size of Ruthenium Metallarectangles
    (2010)
    Barry, Nicolas P.E.
    ;
    Furrer, Julien
    ;
    Therrien, Bruno 
    Cationic (arene)ruthenium-based tetranuclear complexes of the general formula [Ru4(η6-p-cymene)4(μ-N∩N)2(μ-OO∩OO)2]4+ were obtained from the dinuclear (arene)ruthenium complexes [Ru2 (η6-p-cymene)2(μ-OO∩OO)2Cl2] (p-cymene=1-methyl-4-(1-methylethyl)benzene, OO∩OO=5,8-dihydroxy-1,4-naphthoquinonato(2−), 9,10-dihydroxy-1,4-anthraquinonato(2−), or 6,11-dihydroxynaphthacene-5,12-dionato(2−)) by reaction with pyrazine or bipyridine linkers (N∩N=pyrazine, 4,4′-bipyridine, 4,4′-[(1E)-ethene-1,2-diyl]bis[pyridine]) in the presence of silver trifluoromethanesulfonate (CF3SO3Ag) (Scheme). All complexes 4–12 were isolated in good yield as CF3SO3- salts, and characterized by NMR and IR spectroscopy. The host–guest properties of the metallarectangles incorporating 4,4′-bipyridine and (4,4′-[(1E)-ethene-1,2-diyl]bis[pyridine] linkers were studied in solution by means of multiple NMR experiments (1D, ROESY, and DOSY). The largest metallarectangles 10–12 incorporating (4,4′-[(1E)-ethene-1,2-diyl]bis[pyridine] linkers are able to host an anthracene, pyrene, perylene, or coronene molecule in their cavity, while the medium-size metallarectangles 7–9 incorporating 4,4′-bipyridine linkers are only able to encapsulate anthracene. However, out-of-cavity interactions are observed between these 4,4′-bipyridine-containing rectangles and pyrene, perylene, or coronene. In contrast, the small pyrazine-containing metallarectangles 4–6 show no interaction in solution with this series of planar aromatic molecules.