Metallosupramolecular Complexes Through Coordination Chemistry

Chad Mirkin博士，西北大学化学系，由化学学部无机、生物无机和有机金属化学项目资助，主要从事大环和高阶超分子结构的合理设计。主要目标是开发一种新的合成方法，称为“弱链接方法”（WLA），用于从对称半可降解配体和过渡金属构建超分子结构。WLA允许人们合理地设计和制备具有超大尺寸的二维和三维分子结构。此外，它还允许在这样的结构中引入功能。在这个项目中，两类结构的目标是：1)具有合成可编程的结构，化学和光物理性质，具有不同寻常的主客体化学性质的大环多金属化合物；2)用于合成和工业相关反应的新型仿生变构催化剂。1类配合物由配体和金属中心组成，可以控制配合物的大小、形状、水溶性、荧光性和手性。2类配合物将利用这种控制产生具有金属中心排列的超分子化合物，其排列方式是远端位点的反应性将控制催化位点的催化化学。该提案的目标是开发一种新的合成方法来形成非常大的结构，其化学和物理性质可以定制。这些研究的一个主要目的是开发具有潜在有用的光化学和催化性能的新型配合物。这些材料可以应用于有机合成和分子传感器。此外，这些化合物可用于分离，特别是对制药工业重要的手性分子。参与该项目的学生将接受无机和分析方法的培训，本科生将通过利用西北大学现有的REU项目来实现。

Dr. Chad Mirkin, Chemistry Department, Northwestern University, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for the rational design of macrocyclic and higher ordered supramolecular structures. The primary objective is to develop a novel synthetic methodology, termed the "Weak-Link Approach" (WLA), for constructing supramolecular structures from symmetrical hemilabile ligands and transition metals. The WLA allows one to rationally design and prepare two- and three-dimensional molecular architectures with dimensions that are extraordinarily large. Moreover, it allows functionality to be introduced into such structures. In this project, two classes of structures are targeted: 1) macrocyclic multimetallic compounds with synthetically programmable structural, chemical, and photophysical properties with unusual host-guest chemistry, and 2) a new type of biomimetic allosteric catalyst for reactions of both synthetic and industrial relevance. Class 1 complexes will consist of ligands and metal centers that provide control over complex size, shape, water solubility, fluorescence, and chirality. Class 2 complexes will use this control to create supramolecular compounds with arrays of metal centers arranged in such a way that reactivity at a distal site will control catalytic chemistry at a catalytic site. The objectives of this proposal are to develop a novel synthetic approach to form very large structures, whose chemical and physical properties can be tailored. A major aim of these studies is to develop new types of complexes with potentially useful photochemical and catalytic properties. These may have applications in organic synthesis and as molecular sensors. Additionally, these compounds may be useful for separations, particularly of chiral molecules important to the pharmaceutical industry. The students involved in this project will receive training in both inorganic and analytical methodology, and undergraduate participation will be achieved by leveraging existing REU programs at Northwestern.