Binding of 1,5-bis(p-sulfonatophenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacycloocta ne with tetra(methyl viologen) calix[4]resorcinol

作者：Nasybullina G R; Yanilkin V V^*; Nastapova N V; Ziganshina A Yu; Korshin D E; Spiridonova Yu S; Karasik A A; Konovalov A I

来源：Russian Chemical Bulletin, 2012, 61(12): 2295-2310.

DOI：10.1007/s11172-012-0324-y

• calix[4]resorcinol
• methyl viologen
• amphiphilic cyclic diphosphine
• complex
• aggregation
• electroswitchable binding

Binding of an amphiphilic dianion 1,5-bis(p-sulfonatophenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane (APCO(2-)) with an amphiphilic octacation tetra(methyl viologen) calix[4]resorcinol (MVCA(8+)) in media containing different amounts of water and DMSO using NaClO4 or NaCl as supporting electrolytes was shown for the first time by cyclic voltammetry and spectrophotometry. The stoichiometry of the complex depends on the MVCA(8+): APCO(2-) ratio, medium, and supporting electrolyte. A 1: 1 charge-transfer complex is mainly formed (lambda(max) = 480 nm) in 30% DMSO at a ratio of the compounds of 1: 1. A similar 1: 1 complex of APCO(2-) with a model compound methyl viologen MV2+ (lambda(max) = 482 nm) is formed under these conditions. A donor-acceptor interaction occurs between the acceptor viologen units and nitrogen-centered electron-donating fragments of the APCO(2-) dianion. An increase in the content of APCO(2-) in the solution leads to an additional binding of one (30 vol.% DMSO, water, NaClO4) or two (30 vol.% DMSO, water, NaCl) particles of APCO(2-) with the hydrophobic fragments of MVCA(8+). The complexes aggregate to form insoluble precipitates in aqueous and water-DMSO media. A selective reversible electroswitching from the bound to free state of one of the three bound APCO(2-) particles was performed when reducing MVCA(8+) to MVCA(4 center dot+) in a 30 vol.% DMSO/NaCl medium.

• 出版日期2012-12