Metallacrowns: A New Class of Metallamacrocycles

金属大环：一类新的金属大环化合物

• 批准号: 0717098
• 负责人: Vincent Pecoraro
• 金额: $ 52.4万
• 依托单位: Regents of the University of Michigan - Ann Arbor
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-08-01 至 2011-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0717098&HistoricalAwards=false
• 关键词: Metallacrowns; New; Class; Metallamacrocycles

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Vencent L. Pecoraro at the University of Michigan to expand the breadth of metallacrown complexes with regard to the: 1) Preparation of peripherally adorned chiral metallacrowns. 2) Selective recognition of guests in molecular compartments 3) Modular synthesis of chiral solids, and 4) Development of new classes of single molecule magnets. The focus is on the synthesis of 12 and 15 membered metallamacrocycles that have made new chiral solids. These proposed 12-MC-4 and 15-MC-5 molecules may be prepared with a variety of metals, which will allow moderation of the physical properties of the compounds. Chiral 12-MC-4 structures will be prepared using beta-aminohydroxamic acids whereas 15-MC-5 structures will be produced when alpha-aminohydroxamic acids are used. The structure and properties of these metallacrowns can be drastically altered by modifying the sidechains of these aminohydroxamic acids. Sidechains such as benzyl (phenylalanine) or p-hydroxybenzyl (tyrosine) allow formation of metallamacrocyclic dimers in the solid state that can differentially recognize mono and dicarboxylic acids and chiral amino acids. Experiments aim to decorate these cavities with functionalities that will aid selective recognition of other molecules, including chiral carboxylates and alcohols. By changing heteroatom donors of the hydroxamic acids, it is proposed that modification of the metal composition of the metallacrown complexes will be possible. A modular synthetic approach for preparing layered, chiral solids is presented. The observation that metallamacrocycles molecules may act as magnets (single molecule magnetism or SMM) promises use in magnetic storage devices. Chiral recognition by metallacrowns may provide the basis of new methods for separations of chiral molecules using either selective crystallization or chromatographic methods. It may be possible to perform separations of amino acids, amino alcohols or hydroxy acids that are important starting materials for many organic and pharmaceutical syntheses. The modular approach for porous solid synthesis may provide a way to make new catalysts or storage materials.

这个奖项在无机，生物无机和有机化学计划支持教授文森特L。Pecoraro在密歇根大学，以扩大金属冠醚配合物的广度，关于：1）制备周边装饰的手性金属冠醚。2)分子隔室中客体的选择性识别3）手性固体的模块化合成，以及4）新型单分子磁体的开发。重点是合成12和15元金属大环，从而形成新的手性固体。这些提出的12-MC-4和15-MC-5分子可以用各种金属制备，这将允许调节化合物的物理性质。 手性12-MC-4结构将使用β-氨基异羟肟酸制备，而15-MC-5结构将在使用α-氨基异羟肟酸时产生。 这些金属冠醚的结构和性质可以通过修饰这些氨基异羟肟酸的侧链而显著改变。 侧链如苄基（苯丙氨酸）或对羟基苄基（酪氨酸）允许形成固态的金属大环二聚体，其可以区别地识别单羧酸和二羧酸以及手性氨基酸。实验的目的是装饰这些空腔的功能，这将有助于选择性识别其他分子，包括手性羧酸酯和醇。 通过改变异羟肟酸的杂原子供体，提出金属冠醚络合物的金属组成的改性将是可能的。提出了一种制备层状手性固体的模块化合成方法。金属大环分子可以作为磁体（单分子磁性或SMM）的观察结果有望用于磁存储设备。 金属冠醚的手性识别为手性分子的选择性结晶或色谱分离提供了新的方法基础。它可以对氨基酸、氨基醇或羟基酸进行分离，这些是许多有机和药物合成的重要起始材料。多孔固体合成的模块化方法可能提供一种制备新催化剂或存储材料的方法。