Functional Metal-Ligand Assemblies: Reactivity, Self-sorting and Catalysis

人体使用大而复杂的分子，如酶（一种蛋白质）来控制许多细胞过程。化学家努力用人工类似物来模拟这些生物结构的复杂性，但这些模拟物无法接近天然酶的复杂性。自组装是一种强大的方法来创建大型，复杂的分子，而无需复杂的分步合成的挑战。这个过程类似于分子级的乐高积木，可以简单地将单个碎片放在一起，形成更大，更复杂的结构。在这个研究项目中，Hooley教授的目标是开发自组装方法，以创造新的化学结构，以类似于酶的方式发挥作用，并探索这些结构在催化中的潜在应用。该项目为研究生提供跨学科的研究培训，并为代表性不足的本科生提供智力和创造性发展的机会。教育创新与研究相结合，以鼓励本科生和代表性不足的少数民族追求科学事业，并改善加州大学滨江分校的化学课程，重点是提高学生在STEM领域的保留率。自组装笼状配合物可以显示出新颖的材料和传感性能，但简单的分子多面体在其功能应用方面存在局限性。Hooley教授的研究小组试图通过基于金属配体的自组装创造新的功能性合成受体来解决这一问题。本项目主要集中在三个具体领域：1）应用配体的内部功能来控制（通过次级弱相互作用）自组装过程，包括笼状复合物的自分选和化学计量和立体化学的控制; 2）内部官能团的组装后修饰以改变反应性并允许受控，不同多面体几何形状之间的可逆结构切换和笼状配合物的捕获;以及3）这些配合物作为仿生催化剂在串联、正交催化中的应用。在这一领域的一个重要目标是证明笼内部的酸性和碱性功能的螯合允许通常不相容的反应在一个锅中进行。

The human body uses large, complex molecules such as enzymes (a type of protein) to control many cellular processes. Chemists strive to mimic the complexity of these biological structures with artificial analogs, but these mimics cannot approach the complexity of natural enzymes. Self-assembly is a powerful approach to create large, complex molecules without the challenge of complex step-by-step synthesis. This process is similar to molecular-level Lego, whereby individual pieces can be simply put together to make a larger, more complex structure. In this research project, Prof. Hooley aims to develop self-assembly approaches to creating new chemical structures that act in a manner similar to enzymes and to explore the potential applications of these structures in catalysis. This project provides interdisciplinary research training to graduate students and opportunities to underrepresented undergraduates for intellectual and creative development. Educational innovations are integrated with research to encourage undergraduates and underrepresented minorities to pursue careers in science and to improve the chemistry curriculum at UC Riverside with a focus on increasing retention of students in STEM fields. Self-assembled cage complexes can display novel material and sensing properties, but simple molecular polyhedra have limits in their functional applications. Prof. Hooley's research group seeks to remedy this by creating new functional synthetic receptors via metal-ligand based self-assembly. This project focuses on three specific areas: 1) the application of internal functions of ligands to control (via secondary weak interactions) the self-assembly process, including self-sorting and the control of stoichiometry and stereochemistry of cage complexes; 2) post-assembly modifications of internal functional groups to alter reactivity and to allow controlled, reversible structural switching between different polyhedral geometries and trapping of cage complexes; and 3) the application of these complexes as biomimetic catalysts in tandem, orthogonal catalysis. An important objective in this area is to demonstrate that the sequestration of acidic and basic functions in cage interiors allows normally incompatible reactions to be performed in a single pot.