Unsymmetrical Calixcrowns Incorporating Hard and Soft Loops as a New Scaffold for Multinuclear Endo/Exocyclic Complexation and Networking

Abstract

Unsymmerical calix[4]crowns containing [(O(4)S)(O(5))] (L(1)) and [(O(4)S(2))(O(5))] (L(2)) as crown loops were employed as new scaffolds both for complexation studies and for network formation. Reactions of L(1) and L(2) with KI in the presence of CuI afforded a copper(I) iodide cluster linked 1D-type endocyclic dipotassium(I) complex [K(2)(L(1))(Cu(7)I(9))](n) (1) and a copper(I) iodide cluster linked 1D-type endocyclic monopotassium(I) complex [KL(2)(mu(2)-Cu(3)I(4))](n) (2), respectively. By comparison, the reaction of L(2) with KPF(6) in the presence of CuI and HgI(2) afforded the 1-D endocyclic potassium(I) complex [K(L(2))(CuHgI(4))](n) (3), linked with a CuHgI(4) cluster unit. The formation of homo- and heterodinuclear complexes in solution was also confirmed by comparative NMR studies.