London Dispersion as a design element to control molecular structures and chemical reactivity

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The goal of the project is to improve our conceptual understanding of London dispersion (LD) interactions. We strive to achieve this using synthetic, spectroscopic, and computational techniques as follows: a) Synthesis and detailed structural characterization of the re-discovered Gomberg-system (i.e. dimers of trityl derivatives) that are only made possible by using LD interactions; b) determination of a relative scale of dispersion energy donors (DEDs) utilizing "molecular balances" based on hydrocarbons only (cyclooctatetraene and bifluorenylidene derivatives); c) examination of the effects of lipophilic groups (i.e. DEDs) in oligopeptide catalysts as well as substrates in organocatalytic transformations (acylation, Dakin-West reaction). Ideally, the concepts lead to improved ways of directing reactivity and selectivity, novel materials, and the improvement of high-quality quantum mechanical methods for increasingly larger systems. A good part of our work is directly connected to projects of other expert groups from theory and spectroscopy.