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A supramolecular system that switches reversibly, via three different states, through electrochemical adjustment of the guest properties of tetrathiafulvalene (TTF) has been developed. ¹H NMR, luminescence, and absorption spectroscopies, in conjunction with LSI mass spectrometry, X-ray crystallography, and cyclic/differential pulse voltammetries, established that the π-electron-accepting (EA) tetrathiafulvalenium dication (TTF²⁺) binds strongly within the cavity of the π-electron-donating (ED) macrocyclic polyether 1,5-dinaphtho[38]crown-10 (1/5DN38C10), generating a host−guest complex that is stabilized by, inter alia, π−π stacking interactions. Comparable techniques have also demonstrated that neutral tetrathiafulvalene (TTF(0)) acts as an ED guest when it complexes with the EA tetracationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺). On the other hand, the tetrathiafulvalenium radical cation …