Comprehensive models of non-covalent aromatic interactions

非共价芳香族相互作用的综合模型

• 批准号: 1709086
• 负责人: Ken Shimizu
• 金额: $ 46.05万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2020-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1709086&HistoricalAwards=false
• 关键词: Comprehensive; models; non; covalent; aromatic

The weak attractive forces between molecules determine many properties of matter. Examples include melting temperature, degree of expansion upon heating, hardness, and resistance to breaking. Prof. Ken D. Shimizu of the University of South Carolina aims to develop methods to accurately measure and predict these attractive forces between molecules. This project provides research training for graduate and undergraduate students, in particular via collaboration with a faculty member at a women's college and her students. The project also supports the development of an educational website targeted at teaching undergraduate students organic chemistry via a problem based approach. The goal of this project supported by the Macromolecular, Supramolecular and Nanochemistry Program is to develop models that can accurately predict the non-covalent interaction energies of aromatic surfaces such as stacking, edge-to-face, and CH-pi interactions. An innovative aspect of this project is the use of specifically designed molecules to measure these interactions. The versatility of the 'molecular balances' enables the study of a broader range of molecular surfaces and environments and the direct comparison of their attractive or repulsive forces. First, an expansive database of experimentally measured interactions is collected using a 'molecular balance'. The 'balance' flips between two conformational states in which an intramolecular aromatic interaction is formed and broken. Thus, the conformational ratio provides a sensitive and accurate measure of these weak interactions. Second, the importance and magnitude of individual contributing forces to the aromatic interactions is evaluated. Of particular interest are the dispersion and solvophobic terms as their role in solution is still unclear. Finally, a multivariate approach is employed using multiple molecular and solvent descriptors to develop a more accurate predictive model and also to assess the relative strengths of the contributing forces.

分子间的弱吸引力决定了物质的许多性质。 实例包括熔融温度、加热时的膨胀度、硬度和抗断裂性。 Ken D.南卡罗来纳州大学的Shimizu旨在开发精确测量和预测分子间吸引力的方法。 该项目为研究生和本科生提供研究培训，特别是通过与女子学院的一名教员及其学生合作。 该项目还支持开发一个教育网站，旨在通过基于问题的方法教授本科生有机化学。该项目由大分子，超分子和纳米化学计划支持，其目标是开发能够准确预测芳族表面非共价相互作用能的模型，如堆叠，边-面和CH-π相互作用。 该项目的一个创新方面是使用专门设计的分子来测量这些相互作用。 “分子天平”的多功能性使得能够研究更广泛的分子表面和环境，并直接比较它们的吸引力或排斥力。 首先，使用“分子平衡”收集实验测量的相互作用的扩展数据库。 “平衡”在两种构象状态之间翻转，其中分子内芳香相互作用形成和破坏。 因此，构象比提供了这些弱相互作用的灵敏和准确的测量。其次，评价了个体对芳香族相互作用的贡献力的重要性和大小。 特别令人感兴趣的是分散和疏溶剂的条款，因为它们在解决方案中的作用仍然不清楚。 最后，采用多变量方法，使用多个分子和溶剂的描述符，以开发一个更准确的预测模型，并评估贡献力量的相对强度。

项目成果

Anion-enhanced solvophobic effects in organic solvent

有机溶剂中阴离子增强的疏溶剂效应

• DOI: 10.1039/c8cc03964j
• 发表时间: 2018
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Maier, Josef M.;Li, Ping;Ritchey, Jackson S.;Yehl, Christopher J.;Shimizu, Ken D.
• 通讯作者: Shimizu, Ken D.

Guest control of a hydrogen bond-catalysed molecular rotor

• DOI: 10.1039/c7cc07672j
• 发表时间: 2017-11-28
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Rushton, Gregory T.;Vik, Erik C.;Shimizu, Ken D.
• 通讯作者: Shimizu, Ken D.

Study of through-space substituent–π interactions using N -phenylimide molecular balances

使用 N-苯基酰亚胺分子平衡研究空间取代基相互作用

• DOI: 10.1039/c9qo00195f
• 发表时间: 2019
• 期刊: Organic Chemistry Frontiers
• 影响因子: 5.4
• 作者: Hwang, Jungwun;Li, Ping;Vik, Erik C.;Karki, Ishwor;Shimizu, Ken D.
• 通讯作者: Shimizu, Ken D.

Tipping the Balance between S-π and O-π Interactions

• DOI: 10.1021/jacs.8b07617
• 发表时间: 2018-10-17
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Hwang, Jungwun;Li, Ping;Shimizu, Ken D.
• 通讯作者: Shimizu, Ken D.