ORIGINAL ARTICLE Redox-switchable binding of ferrocyanide with tetra(viologen)calix [4] resorcine Gulnaz R. Nasybullina • Vitaliy V. Yanilkin • Natalia V. Nastapova • Dmitry E. Korshin • Albina Y. Ziganshina • Alexandr I. Konovalov Received: 24 September 2010 / Accepted: 22 April 2011 / Published online: 11 May 2011 Ó Springer Science+Business Media B.V. 2011 Abstract A binding of ferrocyanide ([Fe(CN) 6 ] 4- ) with octa-cationic tetra(viologen) calix [4] resorcine (MVCA 8? ) and its ‘‘model’’ compound––dimethyl viologen (MV 2? ) has been studied by cyclic voltammetry in DMSO-H 2 O media (60 vol.% aqueous DMSO, 0.1 M NaClO 4 ). It was found that MV 2? does not interact with ferrocyanide. By contrast, a reversible redox-switchable interaction between [Fe(CN) 6 ] 4- and MVCA 8? has been observed. MVCA 8? forms a 1:1 supramolecular complex MVCA 8? :[Fe(CN) 6 ] 4- with ferrocyanide while its reduced forms (MVCA 4?Á and MVCA 0 ) do not interact with the tetraanion. The switching of the ferrocyanide binding is also observed in the one electron oxidation of [Fe(CN) 6 ] 4- to [Fe(CN) 6 ] 3- . It has been shown, that the calix [4]resorcine in its partial and fully reduced forms and its complex with ferrocyanide form well- defined nanoscale multi-layer films on the electrode surface. Keywords Supramolecular chemistry Á Calixarenes Á Ferrocyanide Á Redox-switching Á Adsorption Introduction Supramolecular systems [1] on the basis of macrocyclic compounds with electrochemically active fragments capa- ble of reversible redox-transitions in the near-field potentials have lately attracted much attention for their using in creation of nanoscale molecular devices with redox-switchable properties. There are many examples of the construction of molecular machines of the catenane and rotaxane type containing electrochemically active building blocks [2–25]. The operation of these molecular mecha- nisms is based on the reversible redox-switchable interac- tion of their buildings blocks. The reversible electron transfer from a donor group or to an acceptor fragment involves a reversible molecular movement of components of the mechanisms due to the fundamental change in the donor–acceptor properties of the components [25]. Redox-active macrocycles are also widely used for the redox-switchable binding of different guest-molecules: inorganic cations [26–28], anions [29–31] or both of the ions [30]. Electrochemically inert macrocycles such as cyclodextrins and cucurbiturils are also applied for the creation of redox-switchable inclusion complexes which are generally operated on the electrochemical reduction or oxidation of guest-molecules (viologen derivatives, tran- sition metal ions, iodide ion) [32–36]. (Thia)calix[n]arenas and calix [4] resorcines, as mac- rocyclic polyphenols, are electrochemically active com- pounds with a tendency for oxidation [37–43]. But these oxidation reactions are reversible only under specific con- ditions, and in most cases they are irreversible. Therefore, the most redox-switchable host–guest complexes of calix- arenes [44–52] operate through redox-active guests. Exceptions are calixarenes with protected hydroxyl groups containing redox-active moieties, for example tetra(meth- ylviologen) calix [4] resorcine (MVCA 8? ). Previously [53], the redox-switchable interaction of MVCA 8? with tetraanionic tetra(sulfonatomethylene)calix [4] resorcine (SCA 4- ) was observed in the DMSO media. The viologen units of MVCA 8? undergo a two-step electrochemical G. R. Nasybullina Á V. V. Yanilkin Á N. V. Nastapova Á D. E. Korshin Á A. Y. Ziganshina (&) Á A. I. Konovalov A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences, Arbuzov str. 8, Kazan, Russian Federation 420088 e-mail: a.ziganshina@yahoo.com V. V. Yanilkin e-mail: yanilkin@iopc.ru 123 J Incl Phenom Macrocycl Chem (2012) 72:299–308 DOI 10.1007/s10847-011-9975-9