Metallosupramolecular Complexes Through Coordination Chemistry

西北大学化学系的查德·米尔金博士得到了化学部无机、生物无机和有机金属化学项目的支持，该项目旨在合理设计大环和更高有序的超分子结构。其主要目标是开发一种新的合成方法，称为“弱连接法”(WLA)，用于从对称的半分子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维度非常大的二维和三维分子结构。此外，它还允许将功能引入此类结构。在这个项目中，目标是两类结构：1)具有可合成的可编程结构、化学和光物理性质的大环多金属化合物，以及2)新型仿生变构催化剂，用于合成和工业相关的反应。1类络合物将由配体和金属中心组成，这些配体和金属中心可以控制络合物的大小、形状、水溶性、荧光和手性。2类络合物将使用这种控制来创建具有金属中心阵列的超分子化合物，其排列方式使得远端位置的反应活性将控制催化位置的催化化学。这项提议的目标是开发一种新的合成方法来形成非常大的结构，其化学和物理性能可以定制。这些研究的一个主要目的是开发具有潜在光化学和催化性能的新型络合物。它们可能在有机合成和作为分子传感器方面有应用。此外，这些化合物可能用于分离，特别是对制药工业重要的手性分子的分离。参与这个项目的学生将接受无机和分析方法的培训，本科生的参与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.