SPP 1807:  Control of London Dispersion Interactions in Molecular Chemistry

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

DFG Programme Priority Programmes

International Connection Austria, Switzerland, USA

• Combined Quantum Chemical and Experimental Study on Metal-Metal Interactions in Heavy Group15 and Group16 Compounds (Applicants Jansen, Georg ;  Schulz, Stephan )
• Competition between hydrogen bonding and dispersion forces in ionic and molecular liquids by means of spectroscopic and thermodynamic methods (Applicants Ludwig, Ralf ;  Verevkin, Sergey )
• Computational determination of accurate bond energies of dispersion-dominated systems in the gas phase (Applicant Klopper, Willem M. )
• Configurations of van der Waals complexes controlled via London dispersion forces as revealed by means of Stark spectroscopy in He-nanodroplets (Applicants Friedrich, Bretislav ;  Slenczka, Alkwin )
• Control of London Dispersion Interactions in Metal-Catalyzed C-H Activation (Applicant Ackermann, Lutz )
• Coordination Funds (Applicant Schreiner, Peter R. )
• Dispersion-Directed Lewis Base Catalysis (Applicant Zipse, Hendrik )
• Dispersion driven isomerism in sigma-bonded acene dimers (Applicant Bettinger, Holger )
• Dispersion Effects on Reactivity and Chemo-, Regio- and Stereoselectivity in Organocatalysed Domino Reactions: A Joint Experimental and Theoretical Study (Applicants Görling, Andreas ;  Tsogoeva, Svetlana )
• Dispersion Interaction in Metal- and Organocatalysis - Assessment and Implementation in Salalen Ligands and N-Heterocyclic Carbenes (Applicant Berkessel, Albrecht )
• Dispersion interactions in fluorinated biopolymers (Applicant Vila Verde, Ana )
• Dispersion interactions in isolated molecules and molecular aggregates analyzed by IR/UV and Raman/UV double resonance spectroscopy (Applicant Riehn, Christoph )
• Experimental and Computational Insights into Dispersion Interactions in Self-Assembled Supramolecular Host-Guest Systems (Applicants Clever, Guido ;  Mata, Ricardo )
• Experimental dissection of dispersion energies from electrostatic contributions and solvent effects in face-to-face pi-stacking complexes (Applicant Biedermann, Frank )
• Heavy main group elements as dispersion energy donors - experimental and theoretical studies of bismuth compounds with bismuth-pi-interactions as structure determining component (Applicants Auer, Alexander A. ;  Mehring, Michael )
• Intra- and intermolecular dispersion forces: Understanding complex formation, aggregation, and the effect of solvation using a bottom-up approach (Applicant Schnell, Melanie )
• Intra- versus intermolecular forces: the influence of solute-solvent interactions on the structure and properties of extended molecules (Applicant Imhof, Petra )
• Intramolecular dispersive interactions in the gas phase: experimental reference data and comparison with solid state and theory (Applicants Berger, Raphael Johann Friedrich ;  Mitzel, Norbert W. )
• Investigation and modelling of dispersion interactions in electronically excited states and the effects of dispersion interactions on electronic excitations (Applicant Hättig, Christof )
• Investigation of London Dispersion Interactions with Azobenzene Switches (Applicant Wegner, Hermann A. )
• Large Dispersion Effects in Organic and Organometallic Thermochemistry, Stereochemistry, and Reaction Mechanisms (Applicant Chen, Peter )
• London Dispersion as a design element to control molecular structures and chemical reactivity (Applicant Schreiner, Peter R. )
• London Dispersion in Brønsted Acid Catalysis (Applicant Gschwind, Ruth M. )
• London Dispersion Interactions inside Macrocycles (Applicant Nau, Werner )
• London vs. Keesom and Debye forces: From FTIR cluster spectroscopy of ambivalent alcohol complexes towards intermolecular energy balances (Applicant Suhm, Martin )
• Modeling of London Dispersion Interactions in Molecular Chemistry (Applicant Grimme, Stefan )
• Quantifying London dispersion effects through novel local correlation techniques (Applicants Bistoni, Giovanni ;  Neese, Frank )
• Stabilization of encounter complexes of intermolecular frustrated Lewis pairs by dispersion energy donors (Applicant Paradies, Jan )
• Stabilization through dispersion interactions? Synthesis and characterization of coordinatively unsaturated metal complexes containing weakly coordinating anionic N-heterocyclic carbene ligands (WCA-NHC) showing metal N-arene interactions (Applicant Tamm, Matthias )
• Understanding the Role of Dispersion Interactions in the Mechanical Properties of Molecular Crystals (Applicant Tkatchenko, Alexandre )

Spokesperson Professor Dr. Peter R. Schreiner