Pyridine-Containing Macrocyclic Complexes and their catalytic applications

Polyazamacrocycles are a common class of macrocyclic compounds, utilized across a number of fields, including, but not limited to, catalysis, selective metal recovery and recycling, therapy and diagnosis, and materials and sensors. Worth of note is their ability to form stable complexes with a plethora of both transition, especially late, and lanthanide metal cations. Deviation of the macrocycle donor atoms from planarity often leads to rather uncommon oxidation states. Both the thermodynamic properties and the complexation kinetics are strongly affected by the introduction of a pyridine moiety into the skeleton of polyazamacrocycles by increasing the conformational rigidity and tuning the basicity. Pyridine-containing ligands engender great interest due to various potential field of applications. They have been successfully employed in biology, Magnetic Resonance Imaging, molecular recognition, supramolecular chemistry and self-assembly, molecular machines and mechanically interlocked architectures. In this lecture, I will provide a perspective on the catalytic applications of metal complexes of pyridine-containing macrocyclic ligands (Pc-L’s) which have been studied in our group (Figure), with a focus interest on the structural features relevant to catalysis. The increased conformational rigidity imposed by the pyridine ring allowed for the isolation and characterization of metal complexes which showed a rich coordination chemistry. The very different conformations accessible upon coordination and the easy tuneable synthesis of the macrocyclic ligands have been exploited in stereoselective syntheses.