FTIR spectra and normal-mode analysis of a tetranuclear Manganese adamantane-like complex in two electrochemically prepared oxidation states: Relevance to the oxygen-evolving complex of Photosystem II
The IR spectra and normal-mode analysis of the adamantane-like compound [Mn4O6(bpea)4]n+ in two oxidation states, MnIV4 and MnIIIMnIV3, that are relevant to the oxygen-evolving complex of photosystem II are presented. Mn-O vibrational modes are identified with isotopic exchange, 16O->18O, of the mono-(mu)-oxo bridging atoms in the complex. IR spectra of the MnIIIMnIV3 species are obtained by electrochemical reduction of the MnIV4 species using a spectroelectrochemical cell, based on attenuated total reflection [Visser et al. Anal Chem 2001, 73, 4374-4378]. A novel method of subtraction is used to reduce background contributions from solvent and ligand modes, and the difference and double-difference spectra are used in identifying Mn-O bridging modes that are sensitive to oxidation state change. Two strong IR bands are observed for the MnIV4 species at 745 and 707 cm-1 and a weaker band at 510 cm-1. Upon reduction, the MnIIIMnIV3 species exhibits two strong IR bands at 745 and 680 cm-1, and several weaker bands are observed in the 510 - 425 cm-1 range. A normal mode analysis is performed to assign all the relevant bridging modes in the oxidized MnIV4 and reduced MnIIIMnIV3 species. The calculated force constants for the MnIV4 species are = 3.15 mdynAngstrom, = 0.55 mdyn/Angstrom, and = 0.20 mdyn/Angstrom. The force constants for the MnIIIMnIV3 species are = 3.10 mdyn/Angstrom, = 2.45 mdyn/Angstrom, = 0.40, and = 0.15 mdyn/Angstrom. This study provides insights for the identification of Mn-O modes in the IR spectra of the photosynthetic oxygen-evolving complex during its catalytic cycle.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Director, Office of Science. Office of Basic Energy Studies. Chemical Sciences, Geosciences, and Biosciences Division; National Institutes of Health (US)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 801949
- Report Number(s):
- LBNL-49912; JACSAT; R&D Project: 448150; B& R KC0600000; TRN: US200223%%469
- Journal Information:
- Journal of the American Chemical Society, Vol. 124, Issue 37; Other Information: Journal Publication Date: 2002; PBD: 19 Mar 2002; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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