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Metal-Organic Frameworks (MOFs) are the subject of intense research focus due to their potential applications in gas storage and separation, biomedicine, energy, and catalysis. Recently, low-valent MOFs (LVMOFs) have been explored for their potential use as heterogeneous catalysts, and multitopic phosphine linkers have been shown as a useful building block for the formation of LVMOFs. However, the synthesis of LVMOFs using phosphine linkers requires conditions that are distinct from the majority of the MOF synthetic literature, including the exclusion of air and water and the use of unconventional modulators and solvents, making it somewhat more challenging to access these materials. This work serves as a general tutorial for the synthesis of LVMOFs with phosphine linkers, including information on: 1) judicious choice of metal precursor, modulator, and solvent; 2) experimental procedures, air-free techniques, and required equipment; 3) proper storage and handling of the resultant LVMOFs; and 4) useful characterization methods for these materials. The intention of this report is to lower the barrier and make more accessible this new subfield of MOF research and facilitate advancements toward novel catalytic materials. 

Low‐valent metal–organic frameworks (LVMOFs) and related materials have gained interest due to their potential applications in heterogeneous catalysis. However, of the few LVMOFs that have been reported, none have shown catalytic activity. Herein, a low‐valent metal‐organic material constructed from phosphine linkers and Ir^Inodes is reported. This material is effectively a crystalline, insoluble analogue of Vaska's complex. As such, the material reversibly binds O₂and catalyzes the reductive formation of enamines from amides.

 

Low‐valent metal–organic frameworks (LVMOFs) and related materials have gained interest due to their potential applications in heterogeneous catalysis. However, of the few LVMOFs that have been reported, none have shown catalytic activity. Herein, a low‐valent metal‐organic material constructed from phosphine linkers and Ir^Inodes is reported. This material is effectively a crystalline, insoluble analogue of Vaska's complex. As such, the material reversibly binds O₂and catalyzes the reductive formation of enamines from amides.

 

Metal–organic frameworks (MOFs) constructed with M⁰nodes are attractive targets due to the reactivity of these low‐valent metals, but examples of these MOFs remain exceedingly rare. The rational design of three‐dimensional MOFs with Pd⁰and Pt⁰nodes using tetratopic phosphine ligands is reported. Five new MOFs have been synthesized by systematic variation of the phosphine ligands and metal precursors employed, and these represent the first examples of MOFs constructed using phosphine–metal bonds as the sole structural component. The MOFs display solid‐state luminescence, with emission maxima that are significantly red‐shifted compared to Pd(PPh₃)₄. In addition, a Rh^Ilow‐valent coordination solid based on the same linker design is reported, which displays solid‐state luminescence that is not observed for the molecular analogue.

 

Metal–organic frameworks (MOFs) constructed with M⁰nodes are attractive targets due to the reactivity of these low‐valent metals, but examples of these MOFs remain exceedingly rare. The rational design of three‐dimensional MOFs with Pd⁰and Pt⁰nodes using tetratopic phosphine ligands is reported. Five new MOFs have been synthesized by systematic variation of the phosphine ligands and metal precursors employed, and these represent the first examples of MOFs constructed using phosphine–metal bonds as the sole structural component. The MOFs display solid‐state luminescence, with emission maxima that are significantly red‐shifted compared to Pd(PPh₃)₄. In addition, a Rh^Ilow‐valent coordination solid based on the same linker design is reported, which displays solid‐state luminescence that is not observed for the molecular analogue.