Outer-sphere association of p-sulfonatothiacalix[4]arene and tetrasulfonatomethylated calix[4]resorcinarene with cobalt(III) tris(dipyridyl): the effect on the spectral and electrochemical properties of the latter

Asiya R Mustafina; Viktoriya V Skripacheva; Aidar T Gubaidullin; Shamil K Latipov; Asiya V Toropchina; Vitaly V Yanilkin; Svetlana E Solovieva; Igor S Antipin; Alexander I Konovalov

doi:10.1021/ic050038i

Outer-sphere association of p-sulfonatothiacalix[4]arene and tetrasulfonatomethylated calix[4]resorcinarene with cobalt(III) tris(dipyridyl): the effect on the spectral and electrochemical properties of the latter

Inorg Chem. 2005 May 30;44(11):4017-23. doi: 10.1021/ic050038i.

Authors

Asiya R Mustafina¹, Viktoriya V Skripacheva, Aidar T Gubaidullin, Shamil K Latipov, Asiya V Toropchina, Vitaly V Yanilkin, Svetlana E Solovieva, Igor S Antipin, Alexander I Konovalov

Affiliation

¹ A. E. Arbuzov Institute of Organic & Physical Chemistry, Arbuzov Street, 8, 420088 Kazan, Russia. asiya@iopc.knc.ru

PMID: 15907130
DOI: 10.1021/ic050038i

Abstract

According to the 1H NMR and X-ray data, the outer-sphere association of [Co(dipy)3]3+ with cyclophanic anions p-sulfonatothiacalix[4]arene and tetrasulfonatomethylated calix[4]resorcinarene is accompanied by the inclusion of the dipyridyl moiety of the former into the cavities of the cyclophanic anions in aqueous and aqueous-DMSO solutions and in the solid state. The first-step dissociation of p-sulfonatothiacalix[4]arene does not change the inclusion mode, but the increase in DMSO content leads to a shallower inclusion of [Co(dipy)3]3+. The electrochemical property changes of [Co(dipy)3]3+ with both receptors undergoing ion pairing indicate the stabilization of the tris(dipyridyl) cobalt complexes in lower oxidation states. The effect of the cyclophanic anions on the cyclic voltammograms of [Co(dipy)3]3+ correlates with the efficiency of binding of the latter with tetrasulfonatomethylated calix[4]resorcinarene and p-sulfonatothiacalix[4]arene.