ArticleProceedings of the National Academy of Sciences of the United States of America2012
Synthetic model of the asymmetric [Mn3CaO4] cubane core of the oxygen-evolving complex of photosystem II.
Article in Proceedings of the National Academy of Sciences of the United States of America, 2012. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 50 papers.
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50 citing papers in PubMed.
- Bimetallic Chemistry by Design: Approaches to the Development of Multifunctional Ligands.Coordination chemistry reviews · 2026Article
- Effective Hamiltonians from Spin-Adapted Configuration Interaction.Journal of chemical theory and computation · 2025Article
- Redox Processes Involving Oxygen: The Surprising Influence of Redox-Inactive Lewis Acids.JACS Au · 2024Review
- Cluster size dependent coordination of formate to free manganese oxide clusters.Physical chemistry chemical physics : PCCP · 2023Article
- Coordination Number in High-Spin-Low-Spin Equilibrium in Cluster Models of the SJournal of the American Chemical Society · 2023Article
- Regeneration and Degradation in a Biomimetic Polyoxometalate Water Oxidation Catalyst.ACS catalysis · 2023Article
- MnInorganic chemistry · 2023Article
- Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions.Chemistry (Weinheim an der Bergstrasse, Germany) · 2022Article
- Mimicking the Oxygen-Evolving Center in Photosynthesis.Frontiers in plant science · 2022Review
- Flexibility Enhances Reactivity: Redox Isomerism and Jahn-Teller Effects in a Bioinspired MnACS catalysis · 2021Article
- CaMnAngewandte Chemie (International ed. in English) · 2021Article
- Phosphate-Templated Encapsulation of a {CoChemSusChem · 2021Article
- Role of redox-inactive metals in controlling the redox potential of heterometallic manganese-oxido clusters.Photosynthesis research · 2021Article
- Article
- Redox Tuning via Ligand-Induced Geometric Distortions at a YMnInorganic chemistry · 2019Article
- Five-coordinate MnProceedings of the National Academy of Sciences of the United States of America · 2019Article
- Giant Heterometallic [MnFrontiers in chemistry · 2019Article
- Tetranuclear [MnJournal of the American Chemical Society · 2018Article
- A Reactive Manganese(IV)-Hydroxide Complex: A Missing Intermediate in Hydrogen Atom Transfer by High-Valent Metal-Oxo Porphyrinoid Compounds.Journal of the American Chemical Society · 2018Article
- Structure and Function of the Photosystem Supercomplexes.Frontiers in plant science · 2018Review
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10 authors.
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Abstract
The laboratory synthesis of the oxygen-evolving complex (OEC) of photosystem II has been the objective of synthetic chemists since the early 1970s. However, the absence of structural information on the OEC has hampered these efforts. Crystallographic reports on photosystem II that have been appearing at ever-improving resolution over the past ten years have finally provided invaluable structural information on the OEC and show that it comprises a [Mn(3)CaO(4)] distorted cubane, to which is attached a fourth, external Mn atom, and the whole unit attached to polypeptides primarily by aspartate and glutamate carboxylate groups. Such a heterometallic Mn/Ca cubane with an additional metal attached to it has been unknown in the literature. This paper reports the laboratory synthesis of such an asymmetric cubane-containing compound with a bound external metal atom, [(1)]. All peripheral ligands are carboxylate or carboxylic acid groups. Variable-temperature magnetic susceptibility data have established 1 to possess an S = 9/2 ground state. EPR spectroscopy confirms this, and the Davies electron nuclear double resonance data reveal similar hyperfine couplings to those of other Mn(IV) species, including the OEC S(2) state. Comparison of the X-ray absorption data with those for the OEC reveal 1 to possess structural parameters that make it a close structural model of the asymmetric-cubane OEC unit. This geometric and electronic structural correspondence opens up a new front in the multidisciplinary study of the properties and function of this important biological unit.
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