Architectural Design of Supramolecular Hosts from Simple Amide/Amine Building Blocks

简单酰胺/胺构建模块的超分子主体的结构设计

• 批准号: 0809736
• 负责人: Kristin Bowman-James
• 金额: $ 45万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2008
• 资助国家: 美国
• 起止时间: 2008-07-01 至 2012-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0809736&HistoricalAwards=false
• 关键词: Architectural; Design; Supramolecular; Hosts; Simple

Award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports Professor Kristin Bowman-James to explore: anion binding, to evaluate the role of lone protons in chemical processes, and the binding and manipulation of neutral triatomic gases. A systematic approach is used by linking a series of similar amide/amine-based hydrogen-bond donor building blocks to give hosts with increasing complexity and dimensionality, and differing degrees of rigidity. The five specific goals are: 1) Simple amide/amine containing hosts will be strategically modified to probe the addition of more hydrogen bonding sites as well as redox switches, the latter using pendant sulfhydryl groups. 2) Structural data on binding of linear and V-shaped anions will be used to expand the project to neutral gases, specifically CO2, N2O, and SO2. Both traditional hydrogen bonding strategies will be used as well as dynamic covalent chemistry (DCC), the formation of covalent bonds that can be readily broken. 3) Complex cyclophane-capped multicycles will be explored as hosts for larger polyanionic guests, including metallates, polyphosphates, nucleotides, and carboxylates. These hosts will provide more rigid architectures than earlier ligands. 4) The prototype phenyl host caps will be replaced by triazine, pyrazine and naphthalene to examine a) the influence of heteroatoms in the preorganization of the side chains and stacking distances, and b) the use of naphthalene to circumvent an acid decomposition of the host with four linkers (tetrad) as well as undesirable intramolecular NHC hydrogen bonds. 5) Structural data indicating that a lone proton could play a role in shaping the conformations of molecules will be pursued to assess the generality of this phenomenon. The goal of this work is to design more complex hosts that will show high affinity for larger and more challenging guests with two targets being neutral gases and single protons. The broader impacts are the educational component that spans students from undergraduate to postdoctoral status, and outreach that includes women and underrepresented minorities. The societal impacts are in understanding not only the complex chemistry involved in anion recognition but also the more elusive targets of neutral gas recognition and the role that lone protons could play in supramolecular and biological chemistry.

无机化学、生物无机化学和金属有机化学奖支持Kristin Bowman-James教授探索：阴离子结合，评估孤立质子在化学过程中的作用，以及中性三原子气体的结合和操纵。一种系统的方法是通过连接一系列类似的基于酰胺/胺的氢键施主构建块来提供具有越来越多的复杂性和维度以及不同刚性程度的宿主。这五个具体目标是：1)简单的含酰胺/胺的主体将被战略性地修饰，以探测更多氢键中心的添加以及氧化还原开关，后者使用侧基的巯基。2)线状和V型阴离子结合的结构数据将用于将该项目扩展到中性气体，特别是二氧化碳、N2O和SO2。将使用传统的氢键策略以及动态共价化学(DCC)，动态共价化学形成的共价键很容易被打破。3)将探索以环番为顶端的复杂多环作为较大的多阴离子客体的宿主，包括金属酸盐、聚磷酸盐、核苷酸和羧酸盐。这些宿主将提供比早期配体更严格的体系结构。4)原型的苯基主体帽将被三嗪、吡嗪和萘取代，以考察a)侧链预组织中杂原子的影响和堆积距离，以及b)使用萘来绕过具有四个连接基的主体的酸分解以及不希望的分子内NHC氢键。5)将利用结构数据来评估这种现象的普遍性，这些数据表明一个孤立的质子可以在塑造分子的构象中发挥作用。这项工作的目标是设计更复杂的主机，以显示出对更大和更具挑战性的客人的高亲和力，两个目标是中性气体和单质子。更广泛的影响是从本科生到博士后学生的教育部分，以及包括女性和代表性不足的少数族裔的外展。社会影响不仅在于了解阴离子识别所涉及的复杂化学，还在于了解中性气体识别的更难以捉摸的目标，以及孤质子在超分子和生物化学中可能发挥的作用。