Crystalline Coordination Networks of Zero-Valent Metal Centers: Formation of a 3‑Dimensional Ni(0) Framework with m‑Terphenyl Diisocyanides

A permanently porous, three-dimensional metal–organic material formed from zero-valent metal nodes is presented. Combination of ditopic m-terphenyl diisocyanide, [CNArMes2]2, and the d10 Ni(0) precursor Ni­(COD)2, produces a porous metal–organic material featuring tetrahedral [Ni­(CNArMes2)4]n structural sites. X-ray absorption spectroscopy provides firm evidence for the presence of Ni(0) centers, whereas gas-sorption and thermogravimetric analysis reveal the characteristics of a robust network with a microdomain N2-adsorption profile.