RESUMEN
We report the synthesis of 14 2,2'-disubstituted 9,9'-bifluorenylidenes as molecular balances for the quantification of London dispersion interactions between various dispersion energy donors. For all balances, we measured ΔGZ/E at 333 K using 1H NMR in seven organic solvents. For various alkyl and aryl substituents, we generally observe a preference for the "folded" Z-isomer due to attractive London dispersion interactions. The cyclohexyl-substituted system shows the largest Z-preference in this study with ΔGZ/E = -0.6 ± 0.05 kcal mol-1 in all solvents, owing to the rotational freedom of cyclohexyl groups paired with their large polarizability that maximizes London dispersion interactions. On the other hand, rigid and sterically more demanding substituents like tert-butyl unexpectedly favor the unfolded E-isomer. This is a result of the close relative position in which the functional groups are positioned in this molecular balance. This close proximity is the reason for the increase of Pauli repulsion in the Z-isomers with large rigid substituents (tert-butyl, adamantyl, and diamantyl) which leads to an equilibrium shift toward the unfolded E-form. While we were able to reproduce most of our experimental trends qualitatively using contemporary computational chemistry methods, quantitative accuracy of the employed methods still needs further improvement.
RESUMEN
We evaluate the use of the cohesive energy density (ced) as a quantitative descriptor for solvophobic effects in organic solvents by measuring ΔGZ/E of the rigid Z- and E-2,2'-diethynyl-9,9'-bifluorenylidene. In line with previously employed balances, solvent-dependent changes in ΔGZ/E are predominantly induced by solvophobic effects, leading to a strong correlation with the solvent's ced. We re-emphasize the role of ceds as quantitative descriptors of solvophobic effects of organic solvents. Our experimental findings are well supported by B3LYP-D3/def2TZVP computations.