Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal–organic framework (MOF) support, NU-1000. The Rh–Ga sites in NU-1000 selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes. The overall stereoselectivity is complementary to the well-known Lindlar’s catalyst, which generates Z-alkenes. The role of the Ga in promoting this unusual selectivity is evidenced by the lack of semihydrogenation selectivity when Ga is absent and only Rh is present in the active site.

NU-1000 is a robust, mesoporous metal-organic framework (MOF) with hexazirconium nodes ([ZrOH], referred to as oxo-Zr nodes) that can be synthesized by combining a solution of ZrOCl·8HO and a benzoic acid modulator in N,N-dimethylformamide with a solution of linker (1,3,6,8-tetrakis(p-benzoic acid)pyrene, referred to as HTBAPy) and by aging at an elevated temperature. Typically, the resulting crystals are primarily composed of NU-1000 domains that crystallize with a more dense phase that shares structural similarity with NU-901, which is an MOF composed of the same linker molecules and nodes. Density differences between the two polymorphs arise from the differences in the node orientation: in NU-1000, the oxo-Zr nodes rotate 120° from node to node, whereas in NU-901, all nodes are aligned in parallel. Considering this structural difference leads to the hypothesis that changing the modulator from benzoic acid to a larger and more rigid biphenyl-4-carboxylic acid might lead to a stronger steric interaction between the modulator coordinating on the oxo-Zr node and misaligned nodes or linkers in the large pore and inhibit the growth of the more dense NU-901-like material, resulting in phase-pure NU-1000. Side-by-side reactions comparing the products of synthesis using benzoic acid or biphenyl-4-carboxylic acid as a modulator produce structurally heterogeneous crystals and phase-pure NU-1000 crystals. It can be concluded that the larger and more rigid biphenyl-4-carboxylate inhibits the incorporation of nodes with an alignment parallel to the neighboring nodes already residing in the crystal.

A heterobimetallic cobalt–aluminum complex was immobilized onto the metal organic framework NU-1000 using a simple solution-based deposition procedure. Characterization data are consistent with a maximum loading of a single Co–Al complex per Zr6 node of NU-1000. Furthermore, the data support that the Co–Al bimetallic complex is evenly distributed throughout the NU-1000 particle, binds covalently to the Zr6 nodes, and occupies the NU-1000 apertures with the shortest internode distances (∼8.5 Å). Heating the anchored Co–Al complex on NU-1000 at 300 °C for 1 h in air completely removes the organic ligand of the complex without affecting the structural integrity of the MOF support. We propose that a Co–Al oxide cluster is formed in place of the anchored complex in NU-1000 during heating. Collectively, the results suggest that well-defined heterobimetallic complexes can be effective precursors for installing two different metals simultaneously onto a MOF support. The CoAl-functionalized NU-1000 samples catalyze the oxidation of benzyl alcohol to benzaldehyde with tert-butyl hydroperoxide as a stoichiometric oxidant. Density functional theory calculations were performed to elucidate the detailed structures of the Co–Al active sites on the Zr6-nodes, and a Co-mediated catalytic mechanism is proposed.

NU-1000, a mesoporous metal-organic framework (MOF) featuring hexazirconium oxide nodes and 3 nm wide channels, was infiltrated with a reactive dicobalt complex to install dicobalt active sites onto the MOF nodes. The anchoring of the dicobalt complex onto NU-1000 occurred with a nearly ideal stoichiometry of one bimetallic complex per node and with the cobalt evenly distributed throughout the MOF particle. To access thermally robust multimetallic sites on an all-inorganic support, the modified NU-1000 materials containing either the dicobalt complex, or an analogous cobalt-aluminum species, were nanocast with silica. The resulting materials feature Co or Co-Al bimetallated hexazirconium oxide clusters within a silica matrix. The cobalt-containing materials are competent catalysts for the selective oxidation of benzyl alcohol to benzaldehyde. Catalytic activity depends on the number of cobalt ions per node, but does not vary significantly between the NU-1000 and silica supports. Hence, the multimetallic oxide clusters remain site-isolated and substrate-accessible within the nanocast materials.