Silver(I) Cage and Infinite Chain Stabilized by Bowl-Shaped Resorcin[4]arene Tetraethynide Ligands

We present a new family of Ag­(I) complexes bearing calixarene-based tetraethynide ligands, namely, [Ag₁₂(L1)₂­·(CH₃CN)₄­·(NO₃)₄]­·2H₂O (1), [Ag₄L1­·(AgCF₃CO₂)₄­·(CH₃OH)] (2), [Ag₄L2·(AgCF₃CO₂)₄]­·H₂O (3), and [Ag₄L3­·(AgCF₃CO₂)₄]­·0.75CH₃COCH₃ (4), which were obtained from the reaction of newly synthesized tetraethynyl functionalized resorcin[4]­arenes with silver­(I) salts. Complex 1 features a 4/m assembly comprising a Ag₁₂ cage sandwiched by two bowl-shaped resorcin[4]­arene tetraethynides, while 2–4 exhibit similar silver­(I) chain structures each stabilized by an alternate attachment of bowl-shaped resorcin[4]­arene tetraethynide units. This work provides the successful example of the use of calixarene-based ligands for the construction of multinuclear silver­(I)–ethynide supramolecular frameworks.