Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes

Abstract

Thiacalixarenes are members of the calixarene family in which sulfur has replaced one or more of the methylene bridges between the phenolic moieties of the macrocycles. Oxidation of the thiacalixarenes leads to sulfinyl and sulfonyl homologs. The incorporation of sulfur affects the metal‐binding affinities of these calixarenes over their all‐carbon analogs through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. Other binding motifs are possible for the oxidized thiacalixarenes leading to a vast array of complexes with metal cations. This chapter covers the literature concerning thiacalixarenes containing free OH groups at the lower rim since they were first reported. Their coordination chemistry toward alkali, alkaline earth, transition, heavy, lanthanide, and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, transition‐metal extraction, and cation transport.

Thiacalix[4]arene-Sandwiched Sandglass-like Ln9 Clusters (Ln = Tb and Eu): Insights into the Selective Luminescence Quenching Properties by p-Nitrobenzene Derivatives

“…Calixarene and derivatives owing cyclic phenol units with a π-rich cavity can be utilized as an organic modification for Ln III to build luminescent LCCs . Among many calixarene analogues, p - tert -butylthiacalix­[4]­arene (H 4 TC4A), containing both phenol oxygen atoms and bridging sulfur atoms, is apt to form M x -TC4A (M, typically divalent transition metals; x = 3 or 4) polynuclear secondary building units (PSBUs) with M-S coordination in various metal clusters .…”