RESUMO
Self-assembly of a flexible tritopic aniline and 3-substituted 2-formylpyridine subcomponents around iron(II) templates gave rise to a low-spin FeII 4 L4 capsule, whereas a high-spin FeII 3 L2 sandwich species formed when a sterically hindered 6-methyl-2-formylpyridine was used. The FeII 4 L4 cage adopted a new structure type with S4 symmetry, having two mer-Δ and two mer-É metal vertices, as confirmed by NMR and X-ray crystallographic analysis. The flexibility of the face-capping ligand endows the resulting FeII 4 L4 framework with conformational plasticity, enabling it to adapt structurally from S4 to T or C3 symmetry upon guest binding. The cage also displayed negative allosteric cooperativity in simultaneously binding different guests within its cavity and at the apertures between its faces.
RESUMO
A "rim-differentiated" pillar[6]arene (RD-P[6]) was obtained successfully, with the assistance of a dimeric silver trifluoroacetate template, among eight different constitutional isomers in a direct and regioselective manner. The solid-state conformation of this macrocycle could switch from the 1,3,5-alternate to a truly rim-differentiated one upon guest inclusion. This highly symmetric RD-P[6] not only hosts metal-containing molecules inside its cavity, but also can form a pillar[6]arene-C60 adduct through co-crystallization on account of donor-acceptor interactions. The development of synthetic strategies to desymmetrize pillararenes offers new opportunities for engineering complex molecular architectures and organic electronic materials.