Anion-pi and halogen-bonded complexes in thermal and photochemical reactions

热和光化学反应中的阴离子-pi 和卤素键配合物

基本信息

批准号：
2003603
负责人：
Sergiy Rosokha
金额：
$ 29.66万
依托单位：
Ball State University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2020
资助国家：
美国
起止时间：
2020-08-15 至 2024-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2003603&HistoricalAwards=false
关键词：
Anion pi halogen bonded complexes

项目摘要

Professor Sergiy Rosokha of Ball State University is supported by the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry to study weak interaction forces between molecules and their role in chemical reactions that need heat or light energy to form products. The specific non-bonding interactions under study (anion-pi and halogen bonding) enable the aggregation of molecules in elaborate supramolecular structures. The project helps define the requirements to efficiently incorporate the non-bonding interactions into molecular design, producing a new tool for more efficient and environmentally benign synthetic procedures for unique chemicals from charged and halogenated molecules, which are ubiquitous in biological systems and the environment. The project is expected to impact many fields, such as drug development, environmental remediation and materials development. The interdisciplinary nature of the project provides a diverse group of undergraduate students in a primarily undergraduate institution with training in a variety of modern experimental chemistry research techniques, as well as computational chemistry. The project builds on the recent findings by Professor Rosokha that, in addition to controlling the structures of supramolecular complexes, anion- and halogen bonding facilitate electron movement between interacting species, which can initiate a variety of chemical transformations. The specific objectives of the project are to identify and characterize halogen bonding and anion-pi complexes in the systems undergoing thermal or light-induced reactions (e.g., halogen and/or electron transfer, nucleophilic substitution, etc.) and to determine the mechanistic role of these complexes in such reactions. To achieve these objectives, the systems in which formation of anion-pi or halogen-bonded complexes is followed by the chemical or photochemical reactions between bonded species, are studied. Transient complexes in such systems are isolated and characterized using low-temperature and stopped-flow UV-Vis measurements and X-ray structural analysis. Together with the measurements of the kinetics of thermal and light-induced reactions, as well as computational analysis, this allows to establish the nature of the intermediate complexes and their role in the reaction mechanisms.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.

鲍尔州立大学的Sergiy Rosokha教授得到了化学划分的大分子，超分子和纳米化学计划，以研究分子之间的弱相互作用力及其在需要热能或光能形成产品的化学反应中的作用。研究中的特定非键相互作用（阴离子PI和卤素键合）使分子在精致的超分子结构中的聚集。该项目有助于定义要求有效地将非键相互作用纳入分子设计中，从而为来自带电和卤代分子的独特化学物质提供了更有效且环保的合成程序，这些工具在生物系统和环境中无处不在。预计该项目将影响许多领域，例如药物开发，环境补救和材料开发。该项目的跨学科性质为小学本科机构中的潜水员提供了一组，并在各种现代实验化学研究技术以及计算化学方面进行了培训。该项目建立在Rosokha教授最近的发现之上，除了控制超分子复合物的结构外，阴离子 - 卤素键和卤素键合有助于相互作用的物种之间的电子运动，还可以引发多种化学转化。该项目的特定物体是识别和表征卤素键合和阴离子 - PI复合物在经历热或光诱导的反应的系统中（例如卤素和/或电子转移，核直类化替代等），并确定这些复合物在此类反应中的机械作用。为了实现这些目标，在键合物种之间形成阴离子-PI或卤素键合复合物的系统之后是化学或光化学反应的系统。使用低温和停止流量的UV-VIS测量和X射线结构分析，将这种系统中的瞬态复合物分离并表征。加上对热反应和光引起的反应动力学的测量以及计算分析，这允许建立中间复合物的性质及其在反应机制中的作用。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识和宽广的影响来通过评估来珍贵的支持。