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A cyclohexyl substituent strongly prefers the chair conformation with large substituents in equatorial positions, while other cycloalkyls are structurally more flexible. In hierarchically formed dimeric titanium(IV) tris(catecholates) equatorial versus axial connection of the cyclohexane to the ester results in either a more compact (axial) or more expanded (equatorial) structure. In DMSO solution the axial position results in a compact structure which minimizes solvophobic effects, leading to higher stability. However, computational investigations indicate that additionally intramolecular London dispersion interactions significantly contribute to the stability of the dimer. Thus, weak side-chain-side-chain interactions are responsible for the high stability of cyclohexyl ester derivatives with axial compared to equatorial ester connection.

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 1 H NMR dimerization constants for the monomer-dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π-π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n-alkyls, n-Ω-alkenyls or n-Ω-alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)