Crystalline Hydrogen-Bonding Networks and Mixed-Metal Framework Materials Enabled by an Electronically Differentiated...

Mixed-metal solid-state framework materials are emerging candidates for advanced applications in catalysis and chemical separations. Traditionally, the syntheses of mixed-metal framework systems rely on postsynthetic ion exchange, metalloligands, or metal-deposition techniques for the incorporation of a second metal within a framework material. However, these methods are often incompatible with the incorporation of low-valent metal centers, which preferentially bind to electronically "soft" ligands according to the tenets of hard/soft acid/base theory. Here we present the electronically differentiated isocyanide/carboxylate heteroditopic linker ligand 1,4-CNAr^Mes2C₆H₄CO₂H (TIB^Mes2H; TIB = terphenyl isocyanide benzoate; Ar^Mes2 = 2,6-(2,4,6-Me₃C₆H₂)₂C₆H₂), which is capable of selective binding of low-valent metals via the isocyano group and complexation of hard Lewis acidic metals through the carboxylate unit. This heteroditopic ligand also possesses an encumbering m-terphenyl backbone at the isocyanide function to foster coordinative unsaturation. The treatment of TIB^Mes2H with [Cu(NCMe)₄]PF₆ in a 3:1 ratio results in preferential binding of the isocyanide group to the Cu(I) center as assayed by multinuclear NMR and IR spectroscopies. IR spectroscopy also provides strong evidence for the formation of a copper(I) tris(isocyanide) complex, wherein the carboxylic acid group remains unperturbed. The addition of TIB^Mes2 to [Cu(NCMe)₄]PF₆ in a 4:1 ratio results in crystallization of the hydrogen-bonding network, [Cu(TIB^Mes2H)₄]PF₆, in which the formation of R₂²(8) hydrogen bonds results in a 7-fold interpenetrated diamondoid lattice structure. The preassembly of a copper(I) tris(isocyanide) complex using TIB^Mes2H, followed by deprotonation and the introduction of ZnCl₂, generates a novel and unusual zwitterionic solid-state phase (denoted as Cu/Zn-^ISOCN-5; ^ISOCN = isocyanide coordination network) consisting of a coordinatively unsaturated [Cu(CNR)₃]⁺ cationic secondary building unit (SBU) and an anionic, paddlewheel-type Zn(II)-based SBU of the formulation [Cl₂Zn₂(O₂CR)₃]^-. Inductively coupled plasma mass spectrometry analysis provided firm evidence for a 2:1 Zn-to-Cu ratio in the network, thereby indicating that the isocyanide and carboxylate groups selectively bind soft and hard Lewis acidic metal centers, respectively. The extended structure of Cu/Zn-^ISOCN-5 is a densely packed, noninterpenetrated AB-stacked layer network with modest surface area. However, it is thermally robust, and its formation and compositional integrity validate the use of an electronically differentiated linker for the formation of mixed-metal frameworks incorporating low-valent metal centers.