title: Encapsulation of ferrocene and peripheral electrostatic attachment of viologens to dimeric molecular capsules formed by an octaacid, deep-cavity cavitand.
abstract: In aqueous media the deep-cavity cavitand octaacid 1 forms stable dimeric molecular capsules 1(2), which are stabilized by hydrophobic effects. In this work we investigate the binding interactions in aqueous solution between these capsules and the redox active guests, ferrocene (Fc) and three 4,4'-bipyridinium (viologen) dications: methyl viologen (MV(2+)), ethyl viologen (EV(2+)), and butyl viologen (BV(2+)). Using NMR spectroscopic and electrochemical techniques we clearly show that the hydrophobic Fc guest is encapsulated inside 1(2). An interesting effect of this encapsulation is that the reversible voltammetric response of Fc is completely eliminated when it resides inside the 1(2) capsular assembly, a finding that is attributed to very slow electrochemical kinetics for the oxidation of Fc@1(2). Diffusion coefficient measurements (PGSE NMR spectroscopy) reveal that all three viologen guests are strongly bound to the dimeric capsules. However, the (1)H NMR spectroscopic data are not consistent with encapsulation and the measured diffusion coefficients indicate that two viologen guests can strongly associate with a single dimeric capsule. Furthermore, the (V(2+))(2)*1(2) complex is capable of encapsulating ferrocene, clearly suggesting that the viologen guests are bound externally, via coulombic interactions, to the anionic polar ends of the capsule. The electrochemical kinetic rate constants for the reduction of the viologen residue in the V(2+)*1(2) complexes were measured and found to be substantially lower than those for the free viologen guests.
authors.affiliation: Center for Supramolecular Science and Department of Chemistry, University of Miami, Coral Gables, FL 33124-0431, USA.
authors.forename: Dagmara
authors.initials: D
authors.lastname: Podkoscielny
authors.forename: Ivy
authors.initials: I
authors.lastname: Philip
authors.forename: Corinne L D
authors.initials: CL
authors.lastname: Gibb
authors.forename: Bruce C
authors.initials: BC
authors.lastname: Gibb
authors.forename: Angel E
authors.initials: AE
authors.lastname: Kaifer