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Investigations of the Effect of the Non-Manganese Metal in Heterometallic-Oxido Cluster Models of the Oxygen Evolving Complex of Photosystem II: Lanthanides as Substitutes for Calcium

Lin, Po-Heng and Takase, Michael K. and Agapie, Theodor (2015) Investigations of the Effect of the Non-Manganese Metal in Heterometallic-Oxido Cluster Models of the Oxygen Evolving Complex of Photosystem II: Lanthanides as Substitutes for Calcium. Inorganic Chemistry, 54 (1). pp. 59-64. ISSN 0020-1669. PMCID PMC4286168. https://resolver.caltech.edu/CaltechAUTHORS:20141222-131120714

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Abstract

We report the syntheses and electrochemical properties of nine new clusters ([LLnMn^(IV)_(3)O_4(OAc)_3(DMF)_n]^+ (Ln = La^3+, Ce^3+, Nd^3+, Eu^3+, Gd^3+, Tb^3+, Dy^3+, Yb^3+, and Lu^3+, n = 2 or 3)) supported by a ligand (L^3–) based on a 1,3,5-triarylbenzene motif appended with alkoxide and pyridine donors. All complexes were obtained by metal substitution of Ca2+ with lanthanides upon treatment of previously reported LMn_3CaO_4(OAc)_3(THF) with Ln(OTf)_3. Structural characterization confirmed that the clusters contain the [LnMn_3O_4] cubane motif. The effect of the redox-inactive centers on the electronic properties of the Mn_3O_4 cores was investigated by cyclic voltammetry. A linear correlation between the redox potential of the cluster and the ionic radii or pKa of the lanthanide metal ion was observed. Chemical reduction of the LMn^(IV)_3GdO_4(OAc)_3(DMF)2 cluster with decamethylferrocene, resulted in the formation of LGdMn^(IV)_2Mn^(III)O_4(OAc)_3(DMF)_2, a rare example of mixed-valence [MMn_3O_4] cubane. The lanthanide-coordinated ligands can be substituted with other donors, including water, the biological substrate.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic5015219DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic5015219PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic5015219PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4286168/PubMed CentralArticle
ORCID:
AuthorORCID
Takase, Michael K.0000-0001-8365-3645
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: June 28, 2014; Published: December 18, 2014. This work was supported by the California Institute of Technology and the NIH R01 GM102687A (T.A.). T.A. is a Sloan, Dreyfus, and Cottrell fellow. We thank Lawrence M. Henling for assistance with crystallography and Zhiji Han for assistance with the characterization of the Ce complexes. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094).
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
NIHR01 GM102687A
NSFCHE-0639094
Issue or Number:1
PubMed Central ID:PMC4286168
Record Number:CaltechAUTHORS:20141222-131120714
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141222-131120714
Official Citation:Investigations of the Effect of the Non-Manganese Metal in Heterometallic-Oxido Cluster Models of the Oxygen Evolving Complex of Photosystem II: Lanthanides as Substitutes for Calcium Po-Heng Lin, Michael K. Takase, and Theodor Agapie Inorganic Chemistry 2015 54 (1), 59-64
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53099
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:23 Dec 2014 17:10
Last Modified:09 Mar 2020 13:19

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