Modular Transition Metal Chalcogenide Coordination Polymers

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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.