We herein report the synthesis and magnetic properties of a Ni(II)-porphyrin tethered to an imidazole ligand through a flexible electron-responsive mechanical hinge. The latter is capable of undergoing a large amplitude and fully reversible folding motion under the effect of electrical stimulation. This redox-triggered movement is exploited to force the axial coordination of the appended imidazole ligand onto the square-planar Ni(II) center, resulting in a change in its spin state from low spin ( = 0) to high spin ( = 1) proceeding with an 80% switching efficiency.
View Article and Find Full Text PDFThis review addresses the synthesis of enantiopure cryptophane and the study of their chiroptical properties. Cryptophane derivatives represent an important class of macrocyclic compounds that can bind a large range of species in solution under different conditions. The overwhelming majority of these host molecules is chiral, and their chiroptical properties have been thoroughly investigated.
View Article and Find Full Text PDFIn this article, we present the synthesis of new cryptophane-type hosts capable of binding xenon in aqueous media and that may be useful for the development of xenon-based magnetic resonance imaging derivatives. The synthetic route proposed was chosen to facilitate both the introduction of water-solubilizing substituents and the functionalization of the host with a single arm showing recognition properties that constitute two crucial steps. This was made possible by preparing new cryptophane-223 derivatives bearing two different chemical functions that can be easily modified at a later stage.
View Article and Find Full Text PDFIn 1,1,2,2-tetrachloroethane-d , the Xe NMR spectrum of the Xe@cryptophane-223 complex bearing seven acetate groups (Xe@1 complex) shows an unusually broad signal compared with that of its congeners (Chapellet, LL. et al. J.
View Article and Find Full Text PDFCryptophanes, cage-molecules constituted of aromatic bowls, are now well recognised as powerful xenon hosts in Xe NMR-based biosensing. In the quest of a dual probe that can be addressed only by NMR, we have studied three cryptophanes bearing a tether with an unsaturated bond. The idea behind this is to build probes that can be detected both via hyperpolarised Xe NMR and para-hydrogen induced polarisation H NMR.
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