RUI: Investigating the Covalency of Intermolecular Interactions and its Effect on the Properties of Supramolecular Complexes.

在化学系大分子、超分子和纳米化学(MSN)计划的支持下，鲍尔州立大学的Sergiy Rosokha将研究超分子相互作用的性质，如阴离子-pi、卤素和硫族键合，这些相互作用在过去20年里引起了化学家的兴趣。利用实验测量和计算分析相结合的方法，Rosokha博士和他的学生将确定共价相互作用对这些成键作用的贡献。这些研究旨在促进化学键概念的发展，并促进这些超分子相互作用在分子识别和环境过程解释中的应用。参与尖端研究项目将为一个以本科生为主的机构的不同本科生群体提供各种现代实验和计算技术的实践经验，并帮助他们为科学事业做好准备。该项目将基于Rosokha博士和他的合作者最近的一项发现，即在卤素和硫化物键合体系中，分子间相互作用有助于共价键之间的连续体。在这个项目中，Rosokha小组将制备阴离子-pi、卤素和硫族键合的络合物，其中的键合强度将通过相互作用物种的明智选择在很大范围内进行调节。结合量子化学计算(能量分解分析、分子中原子的量子理论、键序指数等)，对这些缔合的紫外-可见吸收光谱、核磁共振、电子顺磁共振、傅里叶变换红外光谱和X射线结构进行了详细的研究。将对超分子键中的共价成分进行量化。除了建立控制共价性的贡献及其沿从弱分子间络合物到充分发展的共价键的连续体的变化的因素外，这项研究旨在阐明共价组分对超分子络合物的性质和涉及这些缔合的化学转化的影响，为更有效地应用这些相互作用铺平道路。这一奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Macromolecular, Supramolecular and Nanochemistry (MSN) Program in the Division of Chemistry, Sergiy Rosokha of Ball State University will study the nature of supramolecular interactions such as anion-pi, halogen and chalcogen bondings, interactions that have piqued the interest of chemists over the last two decades. Using a combination of experimental measurements and computational analysis, Dr. Rosokha and his students will determine the contribution of covalent interactions to these bonding interactions. These studies aim to contribute to the development of the concept of chemical bonding and facilitate applications of these supramolecular interactions for molecular recognition and interpretation of environmental processes. Participation in cutting-edge research projects will provide a diverse group of undergraduate students in a primarily undergraduate institution with a hands-on experience in a variety of modern experimental and computational techniques and help prepare them for careers in science. The project will build on a recent finding by Dr. Rosokha and his collaborators of the continuum between intermolecular interactions contributing to the covalent bond in halogen and chalcogen-bonded systems. In this project, the Rosokha group will prepare anion-pi, halogen-, and chalcogen-bonded complexes in which the strength of bonding will be modulated in a wide range by the judicious choice of the interacting species. The scrutiny of the UV-Vis absorbance, NMR (nuclear magnetic resonance), EPR (electron paramagnetic resonance), FT-IR (Fourier transform infrared) spectra and X-ray structures of these associations together with quantum-chemical computations (energy decomposition analysis, quantum theory of atoms in molecules, bond order indices, etc.) will be undertaken to quantify a covalent component in the supramolecular bonding. In addition to establishing factors that control the contribution of covalency and its variation along the continuum from weak intermolecular complexes to fully-developed covalent bonds, this research aims to clarify the effects of covalent components on the properties of the supramolecular complexes and on the chemical transformations involving these associations, paving the way to more efficient applications of these interactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.