SPP 1807: Control of London Dispersion Interactions in Molecular Chemistry

这一建议旨在彻底了解和量化分子体系中的伦敦分散相互作用。分散性是分子聚集的驱动力，在热力学稳定性、分子识别、通过过渡态稳定、蛋白质折叠、酶催化等方面起着关键作用。虽然弥散相互作用有助于使许多常见的现象合理化，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，-吸引的概念还处于初级阶段。该计划的一个主要目标是开发利用分散相互作用构建新的分子结构和化学反应的化学设计原则。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)系统中的分散相互作用。在量化和合理使用色散方面取得成功的机会是极大的，因为只有到了现在，实验和理论能力才达到了能够明确分析色散相互作用的阶段。有许多挑战需要理解和利用色散力来制备新的分子结构，阐明从分子到整体性质的转变，以及通过微调色散能量供体来催化优化过渡态中配体和底物的相互作用。将着重(但不是独家)：结构研究和色散相互作用的量化-通过系统研究量化色散-能量供体-设计和制备新的分子内或分子间色散稳定结构-光激发态中的色散相互作用色散对反应和催化的影响-通过色散能量供体实现过渡态稳定-溶剂诱导的色散相互作用理论和光谱学作为阐明色散相互作用的工具-研究色散相互作用的实验和理论方法的发展-分子光谱学定量色散效应和验证理论结果

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