The electrochemically-driven decomplexation/recomplexation of inclusion adducts of ferrocene derivatives with an electron-accepting receptor

The tetracationic cyclophane, cyclobis(paraquat-4,4'-biphenylene), binds 1,1'-disubstituted ferrocene-based polyethers as a result of (i) [π···π] stacking between the π-electron-deficient bipyridinium units and the π- electron-rich cyclopentadienyl rings and (ii) [C-H···O] hydrogen bonds between the α-bipyridinium hydrogen atoms and the polyether oxygen atoms. However, even the presence of a bulky tetraarylmethane group - which is too large to thread through the cavity of the cyclophane host - at the end of each of the two polyether substituents of the ferrocene-containing guest does not discourage adduct formation of the inclusion type. Thus, in these adducts, the ferrocene unit of the guest is located inside the cavity of the host with its two polyether chains protruding outward from the same side of the host. The alternative pseudorotaxane geometry is not observed in solutions of these 1:1 adducts. The host - guest adducts display absorption bands in the visible spectral region, characteristic of charge-transfer interactions. In the case of one of these adducts, reversible decomplexation/recomplexation takes place upon electrochemical oxidation/reduction of the ferrocene-based unit or upon reduction/oxidation of the tetracationic cyclophane.