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Isocyanide-Based Coordination Networks: Chemical and Structural Stability in Cu(I) and Ni(0) Frameworks


Isocyanide coordination networks (ISOCNs), which feature low-valent metal centers as nodes, are a novel turn for the metal-organic framework (MOF) community. Inspiration was drawn from molecular species to be utilized as motifs for the design of the coordination environment surrounding the low-valent metal node. Specifically, ISOCNs that are synthesized with a phenylene spaced m-terphenyl isocyanide linker (1,4-(CNArMes2)2C6H4) coordinated to d10 Cu(I) and Ni(0) metal centers and the chemical and structural stability in these materials will be the focus of this dissertation. Crystallographic characterization of the framework denoted CuISOCN-4 revealed distinct channels in a Cu(I) tris-isocyanide 2D framework. These channels allow for the solvent exchange of the coordinated Cu-THF for Cu-pyridine molecules to occur despite four-fold interpenetration in the framework. Importantly, a spectroscopic/geometric structure relationship with Cu-ISOCNs was found that could aid future analysis of isocyanide-based materials in chemical reactivity. Single-metal Ni(0)-based nodes supported by tetra-isocyanide coordinated linkers, referred to as NiISOCN-3, were found to undergo a one-electron redox cycle spectroscopically. Additionally, this 3D diamondiod framework presents features of a flexible MOF structure that regains crystallinity upon solvation.

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