1. Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba--Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster.
- Author
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Rouco, Lara, Isabel Fernández-García, M., Pedrido, Rosa, Botana, Luis M., Esteban-Gómez, David, Platas-Iglesias, Carlos, and Maneiro, Marcelino
- Subjects
BIOMIMETIC chemicals ,ARTIFICIAL photosynthesis ,PHOTOCATALYSTS - Abstract
The oxygen-evolving complex (OEC) is the native enzyme that catalyzes the oxidation of water in natural photosynthesis. Two new classes of manganese cluster complexes of formula Ba
2 Mn2 L¹2 (H3 L¹)2 (CH3 OH)4 1 and Mn4 L²6 Cl2 2 were prepared (H4L¹ = N,N0-(ethane-1,2-diyl)bis (2-hydroxybenzamide); L² = methyl picolinimidate) and characterized by standard techniques including microanalysis, IR spectroscopy, ESI spectrometry, and magnetic susceptibility measurements. X-ray diffraction studies of these complexes revealed (i) a box-type structure for 1 formed by two redox-active manganese(III) ions and two barium(II) ions connected by two bridging bisamido-bisphenoxy ligand molecules; and (ii) a planar-diamond array for Mn4 N6 cluster 2 where the picolinimidates act as chelating ligands through the two nitrogen atoms. The ability of 1 and 2 to split water has been studied by means of water photolysis experiments. In these experiments, the oxygen evolution was measured in aqueous media in the presence of p-benzoquinone (acting as the hydrogen acceptor), the reduction of which was followed by UV-spectroscopy. The relevant photolytic activity found for 1 is in contrast to the inactivity of 2 in the photolytic experiments. This different behavior is discussed on the basis of the structure of the biomimetic models and the proposed reaction mechanism for this process supported by DFT calculations. [ABSTRACT FROM AUTHOR]- Published
- 2018
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