Encapsulation of ferrocene and peripheral electrostatic attachment of viologens to dimeric molecular capsules formed by an octaacid, deep-cavity cavitand

Dagmara Podkoscielny, Ivy Philip, Corinne L.D. Gibb, Bruce C. Gibb, Angel E. Kaifer

Research output: Contribution to journalArticle

38 Scopus citations

Abstract

In aqueous media the deepcavity cavitand octaacid 1 forms stable dimeric molecular capsules 12, 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 (MV2+), ethyl viologen (EV2+), and butyl viologen (BV2+). Using NMR spectroscopic and electrochemical techniques we clearly show that the hydrophobic Fc guest is encapsulated inside 12. An interesting effect of this encapsulation is that the reversible voltammetric response of Fc is completely eliminated when it resides inside the 12 capsular assembly, a finding that is attributed to very slow electrochemical kinetics for the oxidation of Fc@12. Diffusion coefficient measurements (PGSE NMR spectroscopy) reveal that all three viologen guests are strongly bound to the dimeric capsules. However, the 1H 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 (V2+)2. 12 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 V2+·12 complexes were measured and found to be substantially lower than those for the free viologen guests.

Original languageEnglish (US)
Pages (from-to)4704-4710
Number of pages7
JournalChemistry - A European Journal
Volume14
Issue number15
DOIs
StatePublished - May 19 2008

Keywords

  • Electrochemistry
  • Ferrocene
  • Molecular capsules
  • Supramolecular chemistry
  • Viologen

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Encapsulation of ferrocene and peripheral electrostatic attachment of viologens to dimeric molecular capsules formed by an octaacid, deep-cavity cavitand'. Together they form a unique fingerprint.

  • Cite this