Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Six States Switching of Redox-Active Molecular Tweezers by Three Orthogonal Stimuli

Six States Switching of Redox-Active Molecular Tweezers by Three Orthogonal Stimuli
Bernold Hasenknopf, Lise-Marie Chamoreau, Valérie Marvaud, Guillaume Vives, Lorien Benda, Jean-Louis Cantin, Benjamin Doistau, Eliseo Ruiz
A six level molecular switch based on terpyridine(Ni-salphen)2 tweezers and addressable by three orthogonal stimuli (metal coordination, redox reaction, and guest binding) is reported. By a metal coordination stimulus, the tweezers can be mechanically switched from an open “W”-shaped conformation to a closed “U”-shaped form. Theses two states can each be reversibly oxidized by the redox stimulus and bind to a pyrazine guest resulting in four additional states. All six states are stable and accessible by the right combination of stimuli and were studied by NMR, XRD, EPR spectroscopy, and DFT calculations. The combination of the supramolecular concepts of mechanical motion and guest binding with the redox noninnocent and valence tautomerism properties of Ni-salphen complexes added two new dimensions to a mechanical switch.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02945

DOI: 10.1021/jacs.7b02945

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