Dec 25, 2015

Spin State as a Marker for the Structural Evolution of Nature's Water-Splitting Catalyst

Inorganic Chemistry
Vera KrewaldNicholas Cox


In transition-metal complexes, the geometric structure is intimately connected with the spin state arising from magnetic coupling between the paramagnetic ions. The tetramanganese-calcium cofactor that catalyzes biological water oxidation in photosystem II cycles through five catalytic intermediates, each of which adopts a specific geometric and electronic structure and is thus characterized by a specific spin state. Here, we review spin-structure correlations in Nature's water-splitting catalyst. The catalytic cycle of the Mn4O5Ca cofactor can be described in terms of spin-dependent reactivity. The lower "inactive" S states of the catalyst, S0 and S1, are characterized by low-spin ground states, SGS = 1/2 and SGS = 0. This is connected to the "open cubane" topology of the inorganic core in these states. The S2 state exhibits structural and spin heterogeneity in the form of two interconvertible isomers and is identified as the spin-switching point of the catalytic cycle. The first S2 state form is an open cubane structure with a low-spin SGS = 1/2 ground state, whereas the other represents the first appearance of a closed cubane topology in the catalytic cycle that is associated with a higher-spin ground state of SGS = 5/2. It ...Continue Reading

Mentioned in this Paper

Calcium [EPC]
Transition Elements
Spin Labels
Drug Substitution
Evolution, Chemical
Chloroplast Photosystem II
Curvature of Spine Associated With Other Conditions

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