SPP 1807: Control of London Dispersion Interactions in Molecular Chemistry

该建议旨在彻底理解和量化分子系统中的伦敦色散相互作用。分散作用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合理化许多常见的现象，如公认的π-π相互作用，但相关的π-π系统的研究要少得多，并且π-π吸引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型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，以定量确定化学（模型）系统中的分散相互作用。成功的量化和合理利用色散的机会是极好的，因为只有现在的实验和理论能力已经达到了一个阶段，允许明确的色散相互作用的分析。有许多挑战，以了解和利用色散力的制备新的分子结构，阐明从分子到散装性质的过渡，并通过微调分散能量供体的催化作用，以优化过渡态的配体和底物的相互作用。将重点讨论以下分主题（但不是唯一的）：色散相互作用的结构研究和量化-通过系统研究对色散能量供体进行量化-新型分子内或分子间色散稳定结构的设计和制备-光激发态下的色散相互作用-色散对反应性和催化作用的影响-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的调制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-解决色散相互作用的实验和理论方法开发-量化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