Utilizing multitopic m-terphenyl isocyanides for the reticular synthesis of organometallic coordination networks, a family of late-transition metal nodes has been developed. Drawing from the molecular version of these materials, the steric bulk of the m-terphenyl isocyanide aids in achieving low-valent, coordinatively unsaturated metal centers. Furthermore, the structural and electronic features that have been found in the analogous molecular species helps to provide insight into the physical properties and chemical reactivity capabilities of these coordination networks. Single-metal-ion Cu(I) node coordination networks were first synthesized due to the ease of handling a bench stable material. These Cu coordination networks were found to readily exchange a labile THF for a more potent pyridine donor, just as in the molecule, despite heavy interpenetration. Moreover, both the highly reactive NiL3 and NiL4 materials were formed under similar solvothermal conditions. Predictively, equimolar reactions do not generate NiL3 material exclusively as was the case for the molecular species where both NiL3 and NiL4 are formed. Interestingly, the doping of a 5% PPh3 solution in the reaction mixture formed only the NiL3 coordination network. These materials have been characterized using single crystal x-ray diffraction and ATR-IR.

Low-valent coordination networks with m-terphenyl isocyanides based linkers

2019 Fall National Meeting

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