SPP 1807: Control of London Dispersion Interactions in Molecular Chemistry

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This proposal aims at a thorough understanding and quantification of London dispersion interactions in molecular systems. Dispersion is the driving force for molecular aggregation that plays a key role in the thermodynamic stability, molecular recognition, chemical selectivity through transition-state stabilization, protein folding, enzyme catalysis etc.. While dispersion interactions help rationalize many common phenonema such as well-established π-π interactions, the related -π systems have been examined much less and the concept of -attraction is in its infancy. A primary goal of this program is the development of chemical design principles that utilizes dispersion interactions in the construction of novel molecular structures and chemical reactions. This can only be achieved through a tight interplay between synthesis, spectroscopy, and theory to quantitatively determine dispersion interactions in chemical (model) systems. The chances of success in the quantification and making rational use of dispersion are excellent because only now the experimental and theoretical capabilities have reached a stage that allow a clear-cut analysis of dispersion interactions. There are many challenges to understand and to utilize dispersion forces for the preparation of novel molecular structures, to elucidate the transition from molecular to bulk properties, and catalysis through fine tuning of dispersion-energy donors for optimizing the interactions of ligands and substrates in transition states. The following subtopics will be emphasized (but are not exclusive): Structural studies and quantification of dispersion interactions - Quantification of dispersion-energy donors through systematic studies - Design and preparation of novel intra- or intermolecularly dispersion-stabilized structures - Dispersion interactions in photoexcited states Dispersion effects on reactivity and in catalysis - Transition-state stabilization through dispersion-energy donors - Solvent-induced modulation of dispersion interactions Theory and spectroscopy as tools for the elucidation of dispersion interactions - Experimental and theoretical method development to address dispersion interactions - Molecular spectroscopy to quantify dispersion effects and validate theoretical results