Kinetic investigation of the dissociation of dinuclear hierarchically assembled titanium(iv) helicates

Abstract

Hierarchically assembled helicates consisting of lithium-bridged triscatecholate titanium(IV) complexes represent a powerful self-assembled supramolecular system with applications as e.g. molecular balances for the evaluation of weak interactions, stereoselectivity switches in asymmetric synthesis or molecular switches. Their applications or properties are based on the monomer–dimer equilibrium which can be easily observed in solution. The dimer is the only species in the crystal. After dissolution, the dimer slowly dissociates into the monomer until the equilibrium is reached. This can be observed by NMR spectroscopy to investigate the kinetics of the dissociation process. A strong steric effect can be observed by studying differently substituted ligands. Activation energies of the dissociation process can be correlated with the size of the ester substituents and the system may be described as a molecular buckle.