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Synthetic and electrochemical studies of heterometallic manganese oxido complexes

Tsui, Emily and Agapie, Theodor (2013) Synthetic and electrochemical studies of heterometallic manganese oxido complexes. In: 245th ACS National Meeting & Exposition, Abstracts of Papers, April 7-11, 2013, New Orleans, LA.

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Redox-inactive metals are important in both biol. electron transfer reactions and in heterogeneous catalysis. A series of high oxidn. state mixed-metal trimanganese dioxido and tetraoxido clusters with incorporated redox-inactive metals of various charge (M = Na^+, Ca^(2+), Sr^(2+), Zn^(2+), Y^(3+), Sc^(3+)) were synthesized. Structural characterization of these clusters using single crystal X-ray diffraction demonstrated that the dioxido clusters contain a conserved [Mn_3M(m_4-O)(m_2-O)] core, while the tetraoxido clusters are contain [MMn_3O_4] cubane clusters of relevance to the cuboidal subsite of the oxygen-evolving complex (OEC) in photosystem II. Electrochem. studies of these cluster show that the redox potentials are linearly correlated to the Lewis acidity of the redox-inactive metal, spanning a window of ca. These results suggest that the Ca^(2+) ion modulates the potential of the OEC, and that other redox-inactive ions may be used to tune the redox potentials of heterogeneous electrocatalysts.

Item Type:Conference or Workshop Item (Paper)
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URLURL TypeDescription website
Tsui, Emily0000-0001-6419-3954
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2013 American Chemical Society.
Record Number:CaltechAUTHORS:20130508-151417953
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:38365
Deposited By: Tony Diaz
Deposited On:12 Aug 2013 22:45
Last Modified:09 Mar 2020 13:19

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