Isocyanide coordination networks CN s), which consist of multitopic isocyanide linker groups and transition-metalbased secondary building units (SBI.Js), are a promising class of organometallic framework materials for the inclusion of low-valent metal centers as primary structural components. Previofisly, it wasdemonstrated that the ditopic m_ terphenyl isocyanide ligand, [CNArme 2 2 2 6-(2,4, -M) C H) could Providesingle-metal'zl n(oAr;esfram=ei:eorks based on Cu(i)6and centers. However, e3C6 2H 3)However, the relatively short, linker,,length in precluded[C,NAI-mes2](2. ien e the formation ofofnetworksthe Itvith s2igntficant porosity. Here, it is shown that ecpansio[CNAlls 2, scaffold with a central PhenY spacer allows for the formation of a robust Cu(1)-based framework with a distinct and solvent accessible channel structure. This new framework1 denoted Cu 4-1-is CN- is prepared as single-clystalline samples from a solvothermal reaction between [Cu(NC114e)4]FF6 and expanded linker 1,4-(CNArivie'2)2C61-14. CrystallograPhic characterization of Cu-Is CN-4 revealed mononuclear [Cu(THF) (C1sTR)3] structural nodes. The expanded diisocyanide linker results in fourfold interpenetrated (6,3) internal morphology However, interpenetration in Cu-isc)CN-4 results in discrete layer domains, each of which Possesses well-defined 29 X 19 A channels along the crystallographic b axis. Tliermogravimetric analysis on Cu-isc)CN-4 revealed THF solvent loss from the channels betvaeeri 100-200 C and dissociation of the Cu-coordinated THF ligand at 290 C. The overall integrity of the network remains intact up to 400 C, thereby signifying the robust nature of materials produced from metal-isocyariide NI -C linkages Aqueous stabilitystudies revealed that Cu-Is CN-4 remains cliemically resistant to exposure to liquid water for several days. In addition, ligand exchange studies in both THF and aqueous solution demonstrate that the Cu -coordinated THF group in Cu-'s CN-4 can be readily substituted with. pyridine. This ligand exchange process occurs via single -crystal -to -single-crystal transformations and can also be readily monitored by infrared spectroscopy.