Modular Transition Metal Chalcogenide Coordination Polymers

模块化过渡金属硫属化物配位聚合物

• 批准号: 2002367
• 负责人: John Anderson
• 金额: $ 46.85万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2002367&HistoricalAwards=false
• 关键词: Modular; Transition; Metal; Chalcogenide; Coordination

Non-Technical Summary Modern society is built on ever increasing technological advances. Recent decades have seen this advancement come from sophisticated processing and engineering perhaps best exemplified by miniaturization largely driven by the surge in nanoscience. Conversely, the discovery of fundamentally new materials has been more limited and many modern innovations rely on classic materials such as bulk silicon. A new class of materials, known as coordination polymers, represent an extremely attractive system for the rational design and tuning of new materials with tailored properties. While there have been dramatic advances in this area, there are still fundamental limitations in the composition of these materials that prevent their use in potentially transformative applications such as renewable energy, next generation electronics, and new magnetic materials. This fundamental research project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, guides the discovery of a novel family of coordination polymers built upon sulfur-based nodes and linkers. Unlike most coordination polymers which rely upon oxygen- or nitrogen-based components, sulfur-based materials exhibit strong interactions between their individual building blocks which enhances their electronic and magnetic properties. Through advances in the fundamental synthetic techniques and an expansive compositional scope, these newly designed materials have the potential to enable new applications in revolutionary technology. In parallel with these research efforts, the principle investigator establishes a local conference in the Chicago area, particularly aimed at including undergraduate students, graduate students, and local postdoctoral researchers. This conference generates a community of researchers in the Chicago area as well as a link to ongoing efforts with younger students to increase scientific communication and literacy. Technical Summary The key fundamental challenge associated with the discovery of new chalcogenide-based coordination polymers is the generation of reliable synthetic protocols for families of novel materials. Such synthetic protocols are relatively well established for more classic coordination polymer materials with carboxylate linkers. Several early examples of chalcogenide-based coordination polymers exhibit remarkable properties and activity, but there is a dearth of these materials compared to their O- and N-based congeners which arises from more poorly understood synthetic protocols. Precise synthetic control over these materials is required to tune morphology, crystallinity, solubility, and electronic structure. This fundamental research project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, establishes the much needed reliable synthetic control that is essential for understanding and tuning bulk properties such as conductivity or magnetism, where defects and grain sizes may have a determinative role on the observed behavior. The synthetic protocols and the resulting family of new materials enables the detailed study of physical properties and more clearly elucidates how the incorporation of chalcogenides mediates enhanced magnetic and electronic coupling. Furthermore, these efforts enable the inclusion of new components into coordination polymers: for example, the researchers study new chalcogenide-based linkers as well as new nodes such as polynuclear chalcogenide clusters. The combination of synthetic access to a variety of new materials and a detailed understanding of their properties enables rational tuning and control over their functionality.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.

现代社会是建立在不断增长的技术进步。近几十年来，这种进步来自复杂的加工和工程，最好的例子可能是主要由纳米科学的激增推动的小型化。相反，新材料的发现更加有限，许多现代创新依赖于经典材料，如体硅。一类新的材料，称为配位聚合物，代表了一个非常有吸引力的系统，用于合理设计和调整具有定制性能的新材料。虽然在这一领域取得了巨大的进步，但这些材料的组成仍然存在根本性的限制，这阻碍了它们在可再生能源，下一代电子产品和新磁性材料等潜在变革性应用中的使用。该基础研究项目由材料研究部的固态和材料化学计划支持，指导发现基于硫基节点和连接体的新型配位聚合物家族。与大多数依赖于氧或氮基组分的配位聚合物不同，硫基材料在其各个结构单元之间表现出强烈的相互作用，这增强了其电子和磁性。通过基本合成技术的进步和广阔的组成范围，这些新设计的材料有可能在革命性技术中实现新的应用。在这些研究工作的同时，主要研究者在芝加哥地区建立了一个地方会议，特别是针对包括本科生，研究生和当地博士后研究人员。本次会议产生了一个研究人员在芝加哥地区的社区，以及与年轻学生正在进行的努力，以增加科学交流和素养的链接。与发现新的硫属化合物基配位聚合物相关的关键基本挑战是为新型材料家族生成可靠的合成方案。此类合成方案对于具有羧酸酯连接基的更经典的配位聚合物材料是相对良好建立的。硫族化合物基配位聚合物的几个早期例子表现出显着的性能和活性，但与它们的O-和N-基同源物相比，这些材料缺乏，这是由于对合成方案的了解更少。需要对这些材料进行精确的合成控制，以调整形态、结晶度、溶解度和电子结构。该基础研究项目由材料研究部的固态和材料化学计划支持，建立了急需的可靠合成控制，这对于理解和调整电导率或磁性等体特性至关重要，其中缺陷和晶粒尺寸可能对观察到的行为起决定性作用。合成方案和由此产生的新材料家族能够详细研究物理性质，并更清楚地阐明硫属化物的掺入如何介导增强的磁耦合和电子耦合。此外，这些努力使配位聚合物中包含新的组分：例如，研究人员研究了新的硫属化合物基连接体以及新的节点，如多核硫属化合物簇。综合利用各种新材料和对其性能的详细了解，可以合理调整和控制其功能。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。