Complexation and Self-Assembling of Sulfonatomethylated Calix[4]resorcinarene with Both Organic and Lanthanide Ions in Aqueous Media

A first report on ternary complex formation between p-sulfonatothiacalix[4]arene, tetramethylammonium ion and gadolinium (III) ion in aqueous solutions

“…Formation of such aggregates on the basis of calix-like ligands in solid state is well documented [2]. We have recently shown [3] that replacement of small guest cations (e.g., N-methylpyridinium or tetramethylammonium) by the long-chained (N-cetylpyridinium or N-cetyltrimethylammonium) ions in their ternary complexes with sulfonatomethylated calix [4]resorcinarene and Gd 3+ ions in aqueous solutions leads to the reversible formation of Gd 3+ -containing assemblies.…”

“…The computational treatment reveals that the following equilibriums, 1 Molar relaxivity, MRR (15 MHz, 298 K), means a paramagnetic contribution to the measured relaxation rate [3,13]. Computer modeling of experimental data was carried out using the CPESSP program (short description and examples of computations are presented in [13]).…”

Supramolecular Assemblies of Sulfonatomethylated Calix[4]resorcinarenes with Aquated Sodium(I), Cesium(I), and Aluminum(III) Ions

“…Generally, molecular capsules and coordination polymers assembled with p ‐sulfonatocalix[4]arene have been reported a lot, [27–33] but coordination complexes based on C4RS are rarely explored. Amirov and co‐workers reported the interaction of tetramethylammonium and N‐methylpyridinium cations with sulfonatomethylated calix[4]resorcinarene in the presence of lanthanide ions resulted in the formation of ternary complexes [34,35] . It is worthy to mention that Maldonado et al have reported the syntheses of two C R ‐tetrasodiumsulfonatomethyleneresorcinarene (R=butyl and 2‐(methylthio)ethyl) as a new example of a linear array of sodium centers and macrocycles [36] …”

Selective Binding Affinity between Quaternary Ammonium Cations and Water-Soluble Calix[4]resorcinarene

“…To date, as representative water-soluble calixarene derivatives, the sulfonated ones that contain phenolic units linked by methylene groups at the ortho positions and modified by sulfonate sites at the para position (SC n As, n = 4–8) have been widely utilized in fluorescent sensing, crystal engineering, virus inhibition, enzyme assays, drug release, and pesticide detoxification, mainly through the synergistic effect with the sulfonate sites at the upper rim and the hydroxyl groups at the lower rim as well as the intrinsic hydrophobic cavity enclosed by phenolic rings. However, in contrast to these known SC n A systems, the research on sulfonated calixarenes and resorcinarenes is unevenly developed, and there is a relative paucity of studies on the molecular binding behaviors of water-soluble resorcinarene tetramers . Consequently, it is imperative to systematically investigate the molecular recognition systems involving water-soluble resorcinarenes, on the basis of which supramolecular cooperativity can be stimulated to facilitate the formation of more advanced nanoassemblies in water.…”