title: Sulfonatocalix[8]arene as a potential reaction cavity: photo- and electro-active dicationic guests arrest conformational equilibrium.
abstract: Smaller members of water-soluble sulfonated calixarenes have been extensively explored in the context of host-guest complexation, supramolecular chemistry, and potential sensors. However, larger members especially eight-membered calixarene (CA[8]) has received much less attention because of its floppy nature and tendency to exist as a mixture of conformational isomers. Our continued interest in identifying molecules with an internal cavity as reaction vessels has led us to examine the host-guest complexation of CA[8] with photoactive bispyridyl ethylenes. We find that 4,4'-bispyridyl ethylene and 3,3'-bispyridyl ethylene upon complexation to CA[8] arrest the conformational equilibrium and force the latter to adopt a single conformation in solution. During complexation, bispyridyl ethylenes are protonated by the sulfonic acid groups of CA[8]. The host-guest complex is stabilized via an electrostatic interaction between the cationic bispyridyl ethylenes and anionic sulfonated calix[8]arene, and we propose the complex to have an inverted capsular structure. This model is also consistent with the electrochemical behavior of 4,4'-dimethylviologen included within CA[8]. Rigidification of bispyridyl ethylenes by the host has a consequence on the excited-state chemistry of the former. Generally, prevalent geometric isomerization of bispyridyl ethylenes are prevented by CA[8] upon complexation.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
authors.forename: Raja
authors.initials: R
authors.lastname: Kaliappan
authors.forename: Yonghua
authors.initials: Y
authors.lastname: Ling
authors.forename: Angel E
authors.initials: AE
authors.lastname: Kaifer
authors.forename: V
authors.initials: V
authors.lastname: Ramamurthy