Hemicubane topological analogs of the oxygen-evolving complex of photosystem II mediating water-assisted propylene carbonate oxidation

Koellner, Connor A.; Gau, Michael R.; Polyak, A. V.; Bayana, Manish; Zdilla, Michael J.

doi:10.1039/d1cc05825h

Cited by 2 publications

(2 citation statements)

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“…Over the years, several biomimetic analogs have been identified which mimic the structural and electronic properties of the inorganic core of Nature’s water oxidation catalyst. − This resulted in synthetic endeavors of a plethora of oxo-bridged oligonuclear complexes, mostly buildup of manganese, displaying beautiful chemical architectures, albeit with less success as compared to the efficiency of the biological water oxidation catalyst . Furthermore, several experimental and synthetic studies have attempted to draw inspiration from the photochemical processes of PSII, to achieve conversion of solar energy into chemical energy and fuels in an elegant manner, rather than mimicking the structural components of the complicated and sophisticated photosynthetic device.…”

Section: Introductionmentioning

confidence: 99%

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Singh,

Roy

2024

ACS Omega

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Increased demand for a carbon-neutral sustainable energy scheme augmented by climatic threats motivates the design and exploration of novel approaches that reserve intermittent solar energy in the form of chemical bonds in molecules and materials. In this context, inspired by biological processes, artificial photosynthesis has garnered significant attention as a promising solution to convert solar power into chemical fuels from abundantly found H 2 O. Among the two redox half-reactions in artificial photosynthesis, the four-electron oxidation of water according to 2H 2 O → O 2 + 4H + + 4e − comprises the major bottleneck and is a severe impediment toward sustainable energy production. As such, devising new catalytic platforms, with traditional concepts of molecular, materials and biological catalysis and capable of integrating the functional architectures of the natural oxygen-evolving complex in photosystem II would certainly be a value-addition toward this objective. In this review, we discuss the progress in construction of ideal water oxidation catalysts (WOCs), starting with the ingenuity of the biological design with earth-abundant transition metal ions, which then diverges into molecular, supramolecular and hybrid approaches, blurring any existing chemical or conceptual boundaries. We focus on the geometric, electronic, and mechanistic understanding of state-of-the-art homogeneous transition-metal containing molecular WOCs and summarize the limiting factors such as choice of ligands and predominance of environmentally unrewarding and expensive noble-metals, necessity of high-valency on metal, thermodynamic instability of intermediates, and reversibility of reactions that create challenges in construction of robust and efficient water oxidation catalyst. We highlight how judicious heterogenization of atom-efficient molecular WOCs in supramolecular and hybrid approaches put forth promising avenues to alleviate the existing problems in molecular catalysis, albeit retaining their fascinating intrinsic reactivities. Taken together, our overview is expected to provide guiding principles on opportunities, challenges, and crucial factors for designing novel water oxidation catalysts based on a synergy between conventional and contemporary methodologies that will incite the expansion of the domain of artificial photosynthesis.

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Section: Introductionmentioning

confidence: 99%

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Singh,

Roy

2024

ACS Omega

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“…Although significant progress has been achieved through extensive biochemical, biophysical, spectroscopic, and structural studies, fundamental questions about this mechanism remain. Synthetic model complexes of appropriate metal oxidation states and cluster geometries for higher S n states are rare but have been demonstrated to complement and benchmark studies on the OEC. − …”

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confidence: 99%

Coordination Number in High-Spin–Low-Spin Equilibrium in Cluster Models of the S₂ State of the Oxygen Evolving Complex

et al. 2023

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The S2 state of the Oxygen Evolving Complex (OEC) of Photosystem II (PSII) shows high-spin (HS) and low-spin (LS) EPR signals attributed to distinct structures based on computation. Five-coordinate MnIII centers are proposed in these species but are absent in available spectroscopic model complexes. Herein, we report the synthesis, crystal structure, electrochemistry, SQUID magnetometry, and EPR spectroscopy of a MnIIIMnIV 3O4 cuboidal complex featuring five-coordinate MnIII. This cluster displays a spin ground state of S = 5/2, while conversion to a six-coordinate Mn upon treatment with water results in a spin state change to S = 1/2. These results demonstrate that coordination number, without dramatic changes within the Mn4O4 core, has a substantial effect on spectroscopy.

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Hemicubane topological analogs of the oxygen-evolving complex of photosystem II mediating water-assisted propylene carbonate oxidation

Abstract: A series of Ca-Mn clusters with the ligand 2-pyridinemethoxide (Py-CH2O) have been prepared with varying degrees of topological similarity to the biological oxygen-evolving complex. These clusters activate water as a...

Cited by 2 publications

References 57 publications

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Coordination Number in High-Spin–Low-Spin Equilibrium in Cluster Models of the S₂ State of the Oxygen Evolving Complex

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Hemicubane topological analogs of the oxygen-evolving complex of photosystem II mediating water-assisted propylene carbonate oxidation

Abstract: A series of Ca-Mn clusters with the ligand 2-pyridinemethoxide (Py-CH2O) have been prepared with varying degrees of topological similarity to the biological oxygen-evolving complex. These clusters activate water as a...

Cited by 2 publications

References 57 publications

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Evolution in the Design of Water Oxidation Catalysts with Transition-Metals: A Perspective on Biological, Molecular, Supramolecular, and Hybrid Approaches

Coordination Number in High-Spin–Low-Spin Equilibrium in Cluster Models of the S2 State of the Oxygen Evolving Complex

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Coordination Number in High-Spin–Low-Spin Equilibrium in Cluster Models of the S₂ State of the Oxygen Evolving Complex