Design and Construction of Metal-Organic Polyhedra

Abstract

This thesis describes the design, synthesis, and characterization of metallosupramolecular capsules and cages from cationic multivalent ligands. In the first half of the thesis, an overview of supramolecular and metallosupramolecular chemistry is provided with short introduction to different families of polyhedra as a basis for metal-organic polyhedra (MOPs). The thesis additionally presents a general design methodologies for the ligands and metal nodes suitable for obtaining supramolecular coordination complexes. This section also presents a brief review of metallosupramolecular cages and capsules obtained using O-donor based anionic ligands.This is followed by a section outlining different strategies used for constructing discrete metallosupramolecular assemblies using N-donor based ligands. Strategies discussed involve two-component systems, utilizing edge-directed and face-directed approaches, together with multicomponent systems and subcomponent systems, with several examples shown. Various applications for supramolecular assemblies, such as storage containers and catalysis or reaction vessels are also demonstrated.The second half of the thesis describes the methods used to synthesize and characterize supramolecular coordination structures obtained in the experimental part of the thesis using cationic multivalent N-donor ligands based on bipyridinium moiety. The assemblies include large supercationic [M₆L₈]³⁶⁺ cage-like assemblies containing Cu^II and Ni^II metal nodes, while encapsulating and coordinating various anions. Additionally, herein this work is reported for the first-time new type of dimeric capsules containing two different types of Zn^II metal nodes.Keywords: metallosupramolecular chemistry, coordination chemistry, structural chemistry, self-assembly, crystallization, X-ray crystallography, N-donor ligands, quaternized ligands