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

奖项在无机，生物无机和有机金属化学计划支持教授克里斯汀鲍曼-詹姆斯探索：阴离子结合，以评估在化学过程中单独质子的作用，以及中性三原子气体的结合和操作。一种系统的方法是通过连接一系列相似的酰胺/胺基氢键供体构建块来增加宿主的复杂性和维度，以及不同程度的刚性。五个具体目标是：1)将对含有简单酰胺/胺的宿主进行战略性修饰，以探测更多氢键位点和氧化还原开关的添加，后者使用悬垂的巯基。2)线性和v形阴离子结合的结构数据将用于将项目扩展到中性气体，特别是CO2， N2O和SO2。传统的氢键策略和动态共价化学（DCC）都将被使用，形成容易断裂的共价键。3)将探索复环环盖多环作为较大的多阴离子客体的宿主，包括金属酸盐、多磷酸盐、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)用三嗪、吡嗪和萘代替原型苯基宿主帽，以检验a)杂原子对侧链预组织和堆积距离的影响，以及b)使用萘来规避带有四个连接体（四联体）和不良分子内NHC氢键的宿主酸分解。结构数据表明，一个单独的质子可以在形成分子的构象中发挥作用，将被追求，以评估这一现象的普遍性。这项工作的目标是设计更复杂的宿主，它将对更大、更具挑战性的客人表现出高亲和力，两个目标是中性气体和单质子。更广泛的影响包括从本科生到博士后的教育组成部分，以及包括女性和未被充分代表的少数民族在内的扩展。社会影响不仅在于理解阴离子识别中涉及的复杂化学，还在于理解中性气体识别中更难以捉摸的目标，以及单个质子在超分子和生物化学中可能发挥的作用。

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.