SPP 1807: Control of London Dispersion Interactions in Molecular Chemistry

这一建议旨在对分子系统中的伦敦色散相互作用进行全面的理解和量化。分散是分子聚集的驱动力，在热力学稳定性、分子识别、过渡态稳定的化学选择性、蛋白质折叠、酶催化等方面起着关键作用。虽然色散相互作用有助于使许多常见现象合理化，例如已建立的π-π相互作用，但相关的-π系统的研究要少得多，并且-吸引力的概念还处于起步阶段。该计划的主要目标是开发化学设计原理，利用分散相互作用构建新的分子结构和化学反应。这只能通过合成、光谱和理论之间的紧密相互作用来实现，以定量地确定化学（模型）系统中的色散相互作用。在量化和合理利用色散方面取得成功的机会很大，因为直到现在，实验和理论能力才达到可以对色散相互作用进行明确分析的阶段。理解和利用色散力来制备新的分子结构，阐明从分子到体性质的转变，以及通过微调色散能供体来优化过渡状态下配体和底物的相互作用，都存在许多挑战。以下子主题将被强调（但不是排他性的）：<s:1>色散相互作用的结构研究和量化-通过系统研究的色散能量供体的量化-新型分子内或分子间色散稳定结构的设计和制备-光激发态中的色散相互作用<s:2>色散对反应性和催化的影响-通过色散能量供体的过渡态稳定-溶剂诱导的色散相互作用调节<s:1>理论和光谱学色散相互作用的阐明。色散相互作用的实验和理论方法的发展。定量色散效应和验证理论结果的分子光谱学

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