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Published March 2015 | public
Journal Article

Synthetic cluster models of the biological oxygen evolving catalyst from photosystem II

Abstract

Redox- inactive metals are found in biol. and heterogeneous water oxidn. catalysts, but their roles are currently not well understood. With current schemes of energy conversion involving water oxidn. and dioxygen redn., a detailed understanding of these systems is imperative for the rational development of practical catalysts. Targeting synthetic model clusters of these catalysts, multinucleating ligands were developed for Earth abundant first- row transition metals (Mn^(2+), Fe^(2+), Co^(2+), Ni^(2+), Cu^(2+), Zn)^(2+). Trimetallic complexes were utilized as precursors to more elaborate metal oxide clusters. Tetranuclear complexes displaying Mn_4, Mn_3Ca and other Mn_3M motifs with varied no. of bridging oxo ligands were synthesized. The redn. potentials of these clusters span a window of over 1 V. With the pK_a of the redox- inactive metal- aqua complex as a measure of Lewis acidity, structurally analogous series of clusters display linear dependence between redn. potential and acidity. These findings provide a general strategy for tuning the clusters over a wide range of potentials and reactivity modes. Implications for the function of biol. and artificial oxygen evolving catalysts will be discussed.

Additional Information

© 2015 American Chemical Society.

Additional details

Created:
August 20, 2023
Modified:
October 23, 2023