{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1362825895804576640.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1073/pnas.1302677110"}},{"identifier":{"@type":"URI","@value":"https://pnas.org/doi/pdf/10.1073/pnas.1302677110"}}],"dc:title":[{"@value":"Reduction potentials of heterometallic manganese–oxido cubane complexes modulated by redox-inactive metals"}],"description":[{"type":"abstract","notation":[{"@value":"<jats:p>\n            Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese–oxido cubane clusters [MMn\n            <jats:sub>3</jats:sub>\n            O\n            <jats:sub>4</jats:sub>\n            ] (M = Sr\n            <jats:sup>2+</jats:sup>\n            , Zn\n            <jats:sup>2+</jats:sup>\n            , Sc\n            <jats:sup>3+</jats:sup>\n            , Y\n            <jats:sup>3+</jats:sup>\n            ) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese–tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese–dioxido clusters. The redox potentials of the [SrMn\n            <jats:sub>3</jats:sub>\n            O\n            <jats:sub>4</jats:sub>\n            ] and [CaMn\n            <jats:sub>3</jats:sub>\n            O\n            <jats:sub>4</jats:sub>\n            ] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn\n            <jats:sub>3</jats:sub>\n            O\n            <jats:sub>2</jats:sub>\n            ] moieties, the present results with more structurally accurate models of the OEC ([MMn\n            <jats:sub>3</jats:sub>\n            O\n            <jats:sub>4</jats:sub>\n            ]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer.\n          </jats:p>"}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1380576197636089984","@type":"Researcher","foaf:name":[{"@value":"Emily Y. Tsui"}],"jpcoar:affiliationName":[{"@value":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125"}]},{"@id":"https://cir.nii.ac.jp/crid/1380576197636089985","@type":"Researcher","foaf:name":[{"@value":"Theodor Agapie"}],"jpcoar:affiliationName":[{"@value":"Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00278424"},{"@type":"EISSN","@value":"10916490"}],"prism:publicationName":[{"@value":"Proceedings of the National Academy of Sciences"}],"dc:publisher":[{"@value":"Proceedings of the National Academy of Sciences"}],"prism:publicationDate":"2013-06-06","prism:volume":"110","prism:number":"25","prism:startingPage":"10084","prism:endingPage":"10088"},"reviewed":"false","url":[{"@id":"https://pnas.org/doi/pdf/10.1073/pnas.1302677110"}],"createdAt":"2013-06-07","modifiedAt":"2022-06-07","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1050303951699506944","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Photocatalytic water oxidation by persulphate with a Ca2+ ion-incorporated polymeric cobalt cyanide complex affording O2 with 200% quantum efficiency"},{"@value":"Photocatalytic water oxidation by persulphate with a Ca<sup>2+</sup> ion-incorporated polymeric cobalt cyanide complex affording O<sub>2</sub> with 200% quantum efficiency"}]},{"@id":"https://cir.nii.ac.jp/crid/1050869456405479424","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@language":"en","@value":"Bio-inorganic hybrid photoanodes of photosystem II and ferricyanide-intercalated layered double hydroxide for visible-light-driven water oxidation"}]},{"@id":"https://cir.nii.ac.jp/crid/1360013168888265344","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Role of redox-inactive metals in controlling the redox potential of heterometallic manganese–oxido clusters"}]},{"@id":"https://cir.nii.ac.jp/crid/1360283693425906816","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"A synthetic Mn\n            <sub>4</sub>\n            Ca-cluster mimicking the oxygen-evolving center of photosynthesis"}]},{"@id":"https://cir.nii.ac.jp/crid/1360285706908910080","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Theoretical Elucidation of Geometrical Structures of the CaMn4O5 Cluster in Oxygen Evolving Complex of Photosystem II Scope and Applicability of Estimation Formulae of Structural Deformations via the Mixed-Valence and Jahn–Teller Effects"}]},{"@id":"https://cir.nii.ac.jp/crid/1360290617837933440","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Pentanuclear Scaffold: A Molecular Platform for Small-Molecule Conversions"}]},{"@id":"https://cir.nii.ac.jp/crid/1360567179946044800","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Lewis Acid Coupled Electron Transfer of Metal–Oxygen Intermediates"}]},{"@id":"https://cir.nii.ac.jp/crid/1360846639396823040","@type":"Article","resourceType":"学術雑誌論文(journal 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