(NO3)3 (terpy = 2,2′:6,2′′- terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltammetry

Clyde W. Cady, Katherine E. Shinopoulos, Robert H. Crabtree, Gary W. Brudvig

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Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO 3)3 [terpy = 2,2′:6′,2′′- terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen.

Original languageEnglish
Pages (from-to)3985-3989
Number of pages5
JournalDalton Transactions
Issue number16
Publication statusPublished - Apr 12 2010


ASJC Scopus subject areas

  • Inorganic Chemistry

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