Reactive Pseudorotaxanes: Inclusion Complexation of Reduced Viologens by the Hosts β‐Cyclodextrin and Heptakis(2,6‐di‐o‐Methyl)‐β‐Cyclodextrin

Abstract

AbstractThe complexation of three guests containing 4,4′‐bipyridinium redoxactive residues by β‐cyclodextrin (β‐CD) and its heptakis‐(2,6‐O‐dimethyl) analogue (DM‐β‐CD) was investigated by means of voltammetric techniques. The three 4,4′‐bipyridinium (viologen) derivatives used as guests were designed to be water‐soluble in all three accessible oxidation states. The N‐substituents chosen to enhance aqueous solubility were: 2‐(2‐(2‐ethoxy)ethoxy)ethanol (guest 12+), 6‐hexanoate (guest 2), and 3‐propanesulfonate (guest 3). Detailed analysis of the voltammetric results by digital simulation techniques revealed that the oxidized forms of the guests did not interact appreciably with either CD host; the two‐electron reduced guests formed extremely stable inclusion complexes, with association constants in the range 103–104M−1, while the cation radical forms exhibited intermediate binding affinities (≈︁102M−1). In all cases, DM‐β‐CD was found to form more stable complexes than unmodified β‐CD.