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Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H + /4e − reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H + /2e − reduction to H 2 O 2 is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxygen to hydrogen peroxide. An established sub-component self-assembly approach was used to synthesize the cubic free-base porphryin topologies from 2-pyridinecarboxaldehyde, tetra-4-aminophenylporphryin (TAPP), and Fe(OTf) 2 (OTf − = trifluoromethansulfonate). Then, a tandem metalation/transmetallation was used to introduce Co( ii ) into the porphyrin faces of the cube, and exchange with the Fe( ii ) cations at the vertices, furnishing a tetrakaideca cobalt cage. Electron paramagnetic resonance studies on a Cu( ii )/Fe( ii ) analogue probed radical interactions which inform on electronic structure. The efficacy and selectivity of the CoCo-cube as a catalyst for hydrogen peroxide generation was investigated using hydrodynamic voltammetry, revealing a higher selectivity than that of a mononuclear Co( ii ) porphyrin (83% versus ∼50%) with orders of magnitude enhancement in standard rate constant ( k s = 2.2 × 10 2 M −1 s −1 versus k s = 3 × 10 0 M −1 s −1 ). This work expands the use of coordination-driven self-assembly beyond ORR to water by exploiting post-synthetic modification and structural control that is associated with this synthetic method. 

Energy-relevant small molecule activations and related processes are often multi-electron in nature. Ferrocene is iconic for its well-behaved one-electron chemistry, and it is often used to impart redox activity to self-assembled architectures. When multiple ferrocenes are present as pendant groups in a single structure, they often behave as isolated sites with no separation of their redox events. Herein, we study a suite of molecules culminating in a self-assembled palladium(II) truncated tetrahedron (TT) with six pendant ferrocene moieties using the iron(III/II) couple to inform about the electronic structure and, in some cases, subsequent reactivity. Notably, although known ferrocene-containing metallacycles and cages show simple reversible redox chemistry, this TT undergoes a complex multi-step electrochemical mechanism upon oxidation. The electrochemical behavior was observed by voltammetric and spectroelectrochemical techniques and suggests that the initial Fc-centered oxidation is coupled to a subsequent change in species solubility and deposition of a film onto the working electrode, which is followed by a second separable electrochemical oxidation event. The complicated electrochemical behavior of this self-assembly reveals emergent properties resulting from organizing multiple ferrocene subunits into a discrete structure. We anticipate that such structures may provide the basis for multiple charge separation events to drive important processes related to energy capture, storage, and use, especially as the electronic communication between sites is further tuned. 

We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co( ii ) porphyrin prism scaffold bridged by Ag( i ) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer (∼35% H 2 O) yet it displays sluggish kinetics, with an order of magnitude lower k s of ∼0.5 M −1 s −1 . The deleterious cofacial effect is not simply due to metal–metal separation, which is similar to our most selective prism catalysts. Instead we conclude the structural rigidity is responsible for these differences. 

The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. Despite their attractive features—including high yielding and facile syntheses, predictable topologies, high stability, and tunability—problematic solubilities have caused ZrMOPs to be under-studied and under-applied. Although these cages have been synthesized with a wide variety of carboxylate-based bridging ligands, we explored a new method for ZrMOP functionalization via node-modification, which we hypothesized could influence solubility. Herein, we report ZrMOPs with benzyl-, vinylbenzyl-, and trifluoromethylbenzyl-pendant groups decorating cyclopentadienyl moieties. The series was characterized by 1 H/ 19 F NMR, high-resolution mass spectrometry, infrared spectroscopy, and single-crystal X-ray diffraction. The effects of node functionalities on ZrMOP solubility were quantified using inductively coupled plasma mass spectrometry. Substitution caused a decrease in water solubility, but for certain organic solvents, e.g. DMF, solubility could be enhanced by ∼20×, from 16 μM for the unfunctionalized cage to 310 μM for the vinylbenzyl- and trifluoromethylbenzyl-cages. 

The known compound K[( PO ) 2 Mn(CO) 2 ] ( PO = 2-((diphenylphosphino)methyl)-4,6-dimethylphenolate) (K[ 1 ]) was protonated to form the new Mn( i ) complex ( HPO )( PO )Mn(CO) 2 ( H 1 ) and was determined to have a p K a approximately equal to tetramethylguanidine (TMG). The reduction potential of K[ 1 ] was determined to be −0.58 V vs. Fc/Fc + in MeCN and allowed for an estimation of an experimental O–H bond dissociation free energy (BDFE O–H ) of 73 kcal mol −1 according to the Bordwell equation. This value is in good agreement with a corrected DFT computed BDFE O–H of 68.0 kcal mol −1 (70.3 kcal mol −1 for intramolecular H-bonded isomer). The coordination of the protonated O-atom in the solid-state H 1 was confirmed using FTIR spectroscopy and X-ray crystallography. The phenol moiety is hemilabile as evident from computation and experimental results. For instance, dissociation of the protonated O-atom in H 1 is endergonic by only a few kcal mol −1 (DFT). Furthermore, [ 1 ] − and other Mn( i ) compounds coordinated to PO and/or HPO do not react with MeCN, but H 1 reacts with MeCN to form H 1 + MeCN . Experimental evidence for the solution-bound O-atoms of H 1 was obtained from 1 H NMR and UV-vis spectroscopy and by comparing the electronic spectra of bona fide 16-e − Mn( i ) complexes such as [{ PNP }Mn(CO) 2 ] ( PNP = − N{CH 2 CH 2 (P i Pr 2 )} 2 ) and [( Me3SiOP )( PO )Mn(CO) 2 ] ( Me3Si 1 ). Compound H 1 is only meta-stable ( t 1/2 0.5–1 day) and decomposes into products consistent with homolytic O–H bond cleavage. For instance, treatment of H 1 with TEMPO resulted in formation of TEMPOH, free ligand, and [Mn II {( PO ) 2 Mn(CO) 2 } 2 ]. Together with the experimental and calculated weakened BDFE O–H , these data provide strong evidence for the coordination and hemilability of the protonated O-atom in H 1 and represents the first example of the phenolic Mn( i )–O linkage and a rare example of a “soft-homolysis” intermediate in the bond-weakening catalysis paradigm.