The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV)h elicates with hydrocarbyle sters 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 HNMR dimerizationc onstants for the monomer-dimer equilibrium show some solvent dependent influenceo ft he side chains on the dimer stability.I nt he dimer,t he ability of the hydrocarbyle ster 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.F urthermore, trends within the different groups of compounds can be observed. For example,t he dimer is destabilized by internal double or triple bonds due to p-p repulsion. As trong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerizationconstants within the series of n-alkyls, n-W-alkenyls or n-W-alkynyls. This corresponds to the interaction of the parenth ydrocarbons, as documented by an even/odd melting point alternation. Figure 1. Wilcox molecular torsion balance. [a] A. Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.Figure 13. Dimerization constantsi n[ D 6 ]DMSOo fb enzyl derivatives Li[Li 3 (4 3 Ti) 2 ].Figure 14. Domains in whicht he dimerization constantso fa lkyl (green), alkenyl (red), alkynyl (blue) and benzyl ester (magenta) substituted complexes Li[Li 3 (L 3 Ti) 2 ]a re observed.

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.