Synthetic control over redox-state and morphology in electronically complex coordination polymers

技术进步是建立在新材料和新方法的发现，以控制其性能和功能。近年来，人们对这类被称为配位聚合物的材料的兴趣激增。这些材料的优点是多孔和可调性极强。除了将这些材料用于气体储存、催化和传感方面的重大进展外，人们越来越关注将其电子特性用于新设备或不同技术中的应用。然而，对配位聚合物的电子性质的理解和控制仍然是有限的。该项目由NSF材料研究部门的固态和材料化学计划支持，具体涉及配位聚合物的合成和研究，这些配位聚合物具有能够保持或失去电子的内在结构单元。调整这些材料的电子学的能力提供了令人兴奋的新特性和应用的希望。此外，这些材料的多孔性允许在比标准材料候选物宽得多的范围内调节其性质。因此，芝加哥大学的研究人员设计了一种广泛的新型材料，具有模块化和可调特性，适用于各种应用。在这些研究工作的同时，该奖项还支持当地的会议，其中包括本科生，研究生和当地的博士后研究人员。本次会议在芝加哥地区建立了一个研究人员社区，并与年轻学生正在进行的努力联系起来，以增加科学交流和素养。 具有导电性和/或磁性等电子特性的配位聚合物（CP）和金属有机框架（MOF）是一类令人兴奋的新材料，具有无数的应用。这些材料的吸引力部分来自其固有特性，即多孔性和网状结构。然而，CP也是独特的电子/磁性材料; CP节点和接头的分子性质使物理性质的合成调整成为可能。此外，与氧化还原活性分子基序耦合的抗衡离子的容易嵌入使得能够实现跨越许多不同氧化还原状态的无与伦比的电子灵活性。这些性质激发了人们对合成新的电子复合物CP和MOFs的极大兴趣。尽管取得了巨大的进展和具有真正显着性能的新材料，但在导电或磁性CP领域仍然存在巨大的合成挑战。也就是说，大多数新合成的材料都是以偶然的氧化态分离的;控制形成的材料的形态，例如将它们纳入设备，仍然是一个重大挑战。现在有一个实质性的需要，调整和控制性能，通过精确的合成调制氧化还原状态和形态。因此，该项目的主要重点是由NSF材料研究部门的固态和材料化学计划支持，旨在发现控制CP氧化还原状态和形态的强大合成方法，特别是在S基材料中。具体来说，芝加哥大学的研究人员探索了氧化还原调节的可变点，无论是在CP合成之前，在CP形成期间原位，还是合成后，以控制电子或磁性。该研究的一个关键假设是CP结构单元或低聚物的溶解度与其氧化还原状态相关，因此与电荷相关，因此氧化还原调节也能够控制CP形态。这项研究的成功实现有望为许多不同领域的电子复杂CP的调整和应用提供一套工具。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

Non-Technical Summary Technological advances are built upon the discovery of new materials and new methods to control their properties and function. Recent years have seen a surge of interest in such a class of materials known as coordination polymers. These materials have the advantage of being porous and extremely tunable. In addition to major advances in using these materials for gas storage, catalysis, and sensing, there is increasing focus on using their electronic properties for applications in new devices or for different technologies. However, understanding and control over the electronic properties of coordination polymers is still limited. This project, which is supported by the Solid State and Materials Chemistry Program in NSF’s Division of Materials Research, specifically involves the synthesis and study of coordination polymers with intrinsic building blocks that have the ability to hold or lose electrons. The ability to tune the electronics of these materials offers the promise of exciting new properties and applications. Furthermore, the porosity of these materials allows the possibility to modulate their properties over a much wider range than standard materials candidates. Thus, researchers at the University of Chicago design a broad new class of materials with modular and tunable properties for a wide variety of applications. In parallel with these research efforts, the award supports a local conference which includes undergraduate students, graduate students, and local postdoctoral researchers. This conference builds a community of researchers in the Chicago area as well as links to ongoing efforts with younger students to increase scientific communication and literacy. Technical Summary Coordination polymers (CPs) and metal-organic-frameworks (MOFs) with electronic properties such as conductivity and/or magnetism are an exciting new class of materials with myriad applications. Part of the appeal of these materials arises from their innate properties, namely porosity and reticular structure. However, CPs are also uniquely poised as electronic/magnetic materials; the molecular nature of CP nodes and linkers enables synthetic tuning of physical properties. Furthermore, facile intercalation of counterions coupled with redox-active molecular motifs enables unparalleled degrees of electronic flexibility spanning many different redox-states. These properties have stimulated immense interest in synthesizing new electronically complex CPs and MOFs. Despite enormous progress and new materials with truly remarkable properties, there remain large synthetic challenges in the field of conducting or magnetic CPs. Namely, most newly synthesized materials are isolated in a serendipitous oxidation state; controlling the morphology of formed materials, for instance to incorporate them into devices, is still a major challenge. There is now a substantial need to tune and control properties via precise synthetic modulation of redox-state and morphology. As such, the main focus of this project, which is supported by the Solid State and Materials Chemistry Program in NSF’s Division of Materials Research, is to discover robust synthetic approaches to control CP redox-state and morphology, particularly in S-based materials. Specifically, researchers at the University of Chicago explore variable points of redox-modulation, either before CP synthesis, in-situ during CP formation, or postsynthetically, to control electronic or magnetic properties. A key hypothesis underlying the research is that the solubility of CP building blocks or oligomers is related to their redox-state and hence charge, and thus that redox modulation also enables control over CP morphology. The successful realization of this research is expected to provide a set of tools for tuning and applying electronically complex CPs in many different areas.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.