Solvent Dependence of the Monomer-Dimer Equilibrium of Ketone-Substituted Triscatecholate Titanium(IV) Complexes.

Hierarchical helicates based on ketone-substituted titanium(IV)triscatecholates show different monomer-dimer behavior depending on different solvents. The dimerization constants of a whole series of differently alkyl-substituted complexes is analyzed to show that the solvent has a very strong influence on the dimerization. Hereby, effects like solvophobicity/philicity, sterics, electronics of the substituents and weak side-chain-side-chain interactions seem to act in concert.

Catechol Thioesters: Ligands for Hierarchically Formed Lithium-Bridged Titanium(IV) Helicates and Helicate-Based Switches.

The thioester moiety is introduced as a lithium binding unit for the hierarchical formation of titanium(IV) catecholate-based lithium-bridged helicates. In solution, the coordination compounds show a monomer-dimer equilibrium which -in comparison to the oxo esters- is significantly shifted towards the monomers. In addition, the influence of the thioester side chain on the dimerization behavior is investigated and an expansible/compressible molecular switch is synthesized.

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution.

The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The H NMR dimerization constants for the monomer-dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability.