Abstract
Most biological and synthetic receptors for small organic molecules employ a combination of relatively weak intermolecular interactions such as hydrogen bonds. A host compound that utilizes stronger yet reversible bonding in a synergistic manner could realize precise recognition, but the regulation and spatial arrangement of such reactive interaction moieties have been a challenge. Here, we show a multinuclear zinc complex synthesized from a macrocyclic ligand hexapap, which inwardly arranges labile metal coordination sites for external molecules. The metallomacrocycle forms a unique wavy-stacked structure upon binding a suitable length of dicarboxylic acids via multipoint coordination bonding. The saddle-shaped deformation and dimerization realize the differentiation of the interaction moieties, and change of guest-binding modes at specific metal coordination sites among the many present have been achieved utilizing acid/base as external stimuli.
Highlights
Most biological and synthetic receptors for small organic molecules employ a combination of relatively weak intermolecular interactions such as hydrogen bonds
Many artificial synthetic receptors[4,5,6] utilizing these interactions have already been developed, but they are still not optimized in terms of specificity
To achieve sophisticated recognition events, it is required to properly and three-dimensionally incorporate multiple interaction moieties into the molecular-binding sites, but chemically synthetic receptors are no match against biological counterparts in that respect
Summary
Most biological and synthetic receptors for small organic molecules employ a combination of relatively weak intermolecular interactions such as hydrogen bonds. The dicarboxylic acids with suitable chain lengths induce the formation of a uniquely-shaped wavy-stacked dimer of the Zn-hexapap via multiple coordination bonds between the carboxylate groups and Zn. the monomeric Zn-hexapap [1Zn6Xn] has six chemically equivalent metal centers, the saddle-shaped deformation and dimerization of the macrocycles realize the differentiation of the Zn(pap) units. This desymmetrized dimeric macrocycle achieves the regulation and change of the guest-binding modes at specific metal coordination sites among the many available utilizing acid/base as external stimuli.
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