New Anions to Understand Recognition Chemistry and Drive Hierarchical Assembly with Cyanostars

在化学系大分子、超分子和纳米化学项目的支持下，印第安纳大学的Amar Flood教授将开展一个项目，了解如何设计分子化合物来捕获带负电荷的离子(负离子)，并使用它们来合成更复杂的化合物。研究阴离子的重要性源于它们的许多全球影响领域，从使用硝酸盐和磷酸盐作为肥料，影响粮食生产和水质，到有机磷酸盐，这是锂离子电池中的主要阴离子。阴离子定向合成的意义来自于大自然对自下而上自组装的使用，并有可能影响纳米制造的未来。计划中的活动将通过培训研究生、本科生和博士后同事在国内和国际上进行研究、交流和合作而造福社会。将制定包容性做法，促进STEM(科学、技术、工程和数学)的多样性和公平性。该项目还有可能通过视频和实验室实验为公众和本科生社区拓宽对阴离子化学的理解。这项研究的成果有望为其他化学领域的研究人员以及需要操纵阴离子的行业提供帮助。在这个关于阴离子识别和阴离子驱动的分级组装的项目中，Amar Flood教授和他的团队将合成一系列阴离子来控制它们的自组装模式，研究它们的氰星大环对阴离子的识别，并研究它们的自组装机制和协作性。该项目有三个目标。目的1通过合成、滴定数据和晶体结构确定三氟硼酸根阴离子上取代基的空间位阻、电子和电荷如何控制氰基星配合物的形成。目的2建立取代磷酸盐的结构与其在氰化星大环内的穿线机理之间的关系，并制备具有串上珠状结构的线状聚合物。AIM 3旨在通过了解如何对阴离子和氰基星形结构进行编程以产生包括网络凝胶、环状聚合物和球形笼子在内的特定结构，来扩大阴离子在分级自组装合成中的作用。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support of the Macromolecular, Supramolecular, and Nanochemistry Program in the Division of Chemistry, Professor Amar Flood of Indiana University will undertake a project to understand how to design molecular compounds to capture negatively charged ions (anions) and use them to synthesize more complex chemical compounds. The significance of studying anions stems from their many global impact areas spanning from the use of nitrate and phosphate as fertilizer, which impact food production and water quality, through to organic phosphates that are the workhorse anions in lithium ion batteries. The significance of anion-directed synthesis is inspired by Nature's use of bottom-up self-assembly and has the potential to impact the future of nano-manufacturing. The planned activity will benefit society by training graduate, undergraduate and postdoctoral coworkers in research, communication and collaboration both nationally and internationally. Inclusive practices will be developed that foster a culture that embraces diversity and equity in STEM (Science, Technology, Engineering and Mathematics). This project also has the potential to broaden understanding of anion-based chemistry for the public and undergraduate communities with videos and laboratory experiments. Outputs from this research are expected to offer benefits to researchers in other areas of chemistry, and to industries that need to manipulate anions.In this project on anion recognition and anion-driven hierarchical assembly, Professor Amar Flood and his team will synthesize a series of anions to control their modes of self-assembly, study their anion recognition by cyanostar macrocycles, and examine their mechanisms and cooperativities of self-assembly. The project has three Aims. Aim 1 seeks to determine how the sterics, electronics and charge of substituents on anions composed of trifluoroborates control formation of cyanostar complexes by using synthesis, titration data and crystal structures. Aim 2 aims to establish the correlation between the structures of substituted phosphates and their mechanisms of threading inside cyanostar macrocycles and to make threaded polymers with beads-on-a-string structures. Aim 3 seeks to expand the role of anions in hierarchical self-assembly synthesis by understanding how anions and cyanostar structures need to be programmed to produce specific architectures that include network gels, cyclic polymers, and spherical cages.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.