Preparation and Development of Metal-Isocyanide Framework Materials

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Non-technical AbstractWith this project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, Professor Joshua S. Figueroa and his research team at the University of California, San Diego develop a new class of metal/organic hybrid solid-state materials. There is significant current interest in the development of solid-state materials with advanced function and properties for a range of technological and industrial applications, including chemical separations, chemical storage, energy harvesting and chemical catalysis. Among such materials, Metal-Organic Frameworks (MOFs), which are a type of hybrid inorganic/organic solid-state material, are a standout. The reason for this is because MOFs can be prepared with diverse structures, for example with different inorganic portions of the material, and it is relatively easy to tune the organic component for specific applications. While the synthetic and materials chemistry aspects of MOFs have significantly advanced over the past two decades, a common paradigm is followed for their preparation. This involves the interaction of oxidized metal centers with anionic organic linker groups. From a fundamental perspective, this particular constitution limits the chemical and physical properties of the materials, especially from the perspective of mediating chemical or adsorptive processes that rely on the presence of metal centers with high electron counts. In this respect, this project establishes a class of neutral linker groups for the routine and reliable incorporation of electron-rich metal centers into network materials. The scientific work of this award is augmented by a significant effort to broaden participation of junior- and community-college transfer student participation in materials science research at the University of California, San Diego, as well as to introduce local San Diego Area high school students to modern aspects of materials science research.Technical AbstractWith support from the Solid State and Materials Chemistry Program in the Division of Materials Research, Professor Joshua S. Figueroa of the University of California, San Diego explores the synthesis and properties of isocyanide coordination networks featuring low-valent metal centers as secondary building units (SBUs). Organoisocyanides are well established to form robust metal-ligand linkages via strong sigma-donation and highly efficient pi-backbonding interactions. This electronic duality has also been long recognized to stabilize low-valent metal centers. Seeking to transport these discrete molecular properties into a network-materials context, synthetic investigations are undertaken to prepare porous, three-dimensional solid-state networks featuring low-valent transition metal nodes using multi-topic isocyanide linkers. Furthermore, in an effort to simultaneously impart coordinative saturation on the metal nodes of these materials, the m-terphenyl isocyanide ligand topology are a predominant feature of these studies. Newly prepared isocyanide coordination networks are investigated in the context of their fundamental materials properties. An emphasis is placed on chemiabsorptive properties of these materials as function of the low-valent metal center incorporation. The experimental work undertaken as part of this award is complemented by an educational program targeting the early inclusion of junior/community college transfer students at the University of California, San Diego in materials science research. The goal of these efforts is to increase participation of a broader student demographic in STEM research and advanced training. Lastly, to augment training experiences for students working on this project, outreach to local area high schools in the form of curriculum augmentation is also a major component of the project.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.