Molecular Wind-Up Meter for the Quantification of London Dispersion Interactions.

ConspectusThe experimental quantification of interactions on the molecular level provides the necessary basis for the design of functional materials and chemical processes. The interplay of multiple parameters and the small quantity of individual interactions pose a special challenge for such endeavors. The common method is the use of molecular balances, which can exist in two different states. Thereby, a stabilizing interaction can occur in one of the states, favoring its formation and thus affecting the thermodynamic equilibrium of the system. One challenge is determining the change in this equilibrium since various analytical methods could not be applied to fast-changing equilibria. A new and promising method for quantifying molecular interactions is the use of Molecular Wind-up Meters (MWM) in which the change in kinetics, rather than the effect on thermodynamics, is investigated. An MWM is transformed with an energy input (e.g. irradiation) into a metastable state. Then, the rate of thermal transformation back to the ground state is measured. The strength of interactions present in the metastable state controls the kinetics of the back reactions, allowing direct correlation. The advantage of this approach lies in the high sensitivity (energy differences can be larger by 1 order of magnitude) and, in general, allows the use of a broader range of solvents and analytical methods. An Azobenzene-based MWM has been established as a powerful tool to quantify London dispersion interactions. London dispersion (LD) represents the attractive part of the van der Waals potential. Although neglected in the past due to its weak character, it has been shown that the influence of LD on the structure, stability, and reactivity of matter can be decisive. Especially in larger molecules, its energy contribution increases overproportionately with the number of atoms, which has sparked increasing interest in the use of so-called dispersion energy donors (DED) as a new structural element. Application of the azobenzene-based MWM not only allowed the differentiation of bulkiness, but also systematically addressed the influence of the length of -alkyl chains. Additionally, the solvent influence on LD was studied. Based on the azobenzene MWM, an increment system has been proposed, allowing a rough estimate of the effect of a specific DED.