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

Abstract

Interactions of C‐iso‐butyl‐calix[4]resorcinarene (1) with sodium sulfite and formaldehyde solution gave a new water‐soluble sulfonatomethylated calix[4]resorcinarene (C4RS) 2 in a quantitative yield. Treatment of 2 with NaOH in a mixture of water, acetonitrile, and methanol afforded complex [Na4(C4RS‐4H)(CH3CN)(H2O)6]2⋅CH3OH (3). Reaction of 2 with NaOH aqueous solution, followed by addition of cesium chloride, led to isolation of complex Cs4Na[(C4RS)2‐5H)](H2O)2 (4). Cation exchange of aluminum nitrate hydrate with complex 3 afforded complex {Al3(H2O)5[(C4RS)2‐9H)]}2⋅(C2H5OH)2⋅(H2O)4 (5). The three new coordination complexes 3–5 were characterized by single crystal X‐ray diffraction analysis. Complexes 3 and 4 display a two‐dimensional bilayer structure through bridging of the sulfonate groups by sodium/cesium cations. The aluminum sulfonatomethylated calix[4]resorcinarene sheets in complex 5 are associated in a one‐dimensional bilayer arrangement and further connected by hydrogen bonds to form a two‐dimensional network.