A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II.

Protonation states of water ligands and oxo bridges are intimately involved in tuning the electronic structures and oxidation potentials of the oxygen evolving complex (OEC) in Photosystem II, steering the mechanistic pathway, which involves at least five redox state intermediates S(n) (n = 0-4) resulting in the oxidation of water to molecular oxygen. Although protons are practically invisible in protein crystallography, their effects on the electronic structure and magnetic properties of metal active sites can be probed using spectroscopy. With the twin purpose of aiding the interpretation of the complex electron paramagnetic resonance (EPR) spectroscopic data of the OEC and of improving the view of the cluster at the atomic level, a complete set of protonation configurations for the S(2) state of the OEC were investigated, and their distinctive effects on magnetic properties of the cluster were evaluated. The most recent X-ray structure of Photosystem II at 1.9 Å resolution was used and refined to obtain the optimum structure for the Mn(4)O(5)Ca core within the protein pocket. Employing this model, a set of 26 structures was constructed that tested various protonation scenarios of the water ligands and oxo bridges. Our results suggest that one of the two water molecules that are proposed to coordinate the outer Mn ion (Mn(A)) of the cluster is deprotonated in the S(2) state, as this leads to optimal experimental agreement, reproducing the correct ground state spin multiplicity (S = 1/2), spin expectation values, and EXAFS-derived metal-metal distances. Deprotonation of Ca(2+)-bound water molecules is strongly disfavored in the S(2) state, but dissociation of one of the two water ligands appears to be facile. The computed isotropic hyperfine couplings presented here allow distinctions between models to be made and call into question the assumption that the largest coupling is always attributable to Mn(III). The present results impose limits for the total charge and the proton configuration of the OEC in the S(2) state, with implications for the cascade of events in the Kok cycle and for the water splitting mechanism.

The identification of a unique intermediate in biological water oxidation establishes the water binding mechanism in the S2 to S3 state transition.

The S2 state of the oxygen-evolving complex of photosystem II, which consists of a Mn4O5Ca cofactor, is EPR-active, typically displaying a multiline signal, which arises from a ground spin state of total spin ST = 1/2. The precise appearance of the signal varies amongst different photosynthetic species, preparation and solvent conditions/compositions. Over the past five years, using the model species Thermosynechococcus elongatus, we have examined modifications that induce changes in the multiline signal, i.e. Ca(2+)/Sr(2+)-substitution and the binding of ammonia, to ascertain how structural perturbations of the cluster are reflected in its magnetic/electronic properties. This refined analysis, which now includes high-field (W-band) data, demonstrates that the electronic structure of the S2 state is essentially invariant to these modifications. This assessment is based on spectroscopies that examine the metal centres themselves (EPR, (55)Mn-ENDOR) and their first coordination sphere ligands ((14)N/(15)N- and (17)O-ESEEM, -HYSCORE and -EDNMR). In addition, extended quantum mechanical models from broken-symmetry DFT now reproduce all EPR, (55)Mn and (14)N experimental magnetic observables, with the inclusion of second coordination sphere ligands being crucial for accurately describing the interaction of NH3 with the Mn tetramer. These results support a mechanism of multiline heterogeneity reported for species differences and the effect of methanol [Biochim. Biophys. Acta, Bioenerg., 2011, 1807, 829], involving small changes in the magnetic connectivity of the solvent accessible outer MnA4 to the cuboidal unit Mn3O3Ca, resulting in predictable changes of the measured effective (55)Mn hyperfine tensors. Sr(2+) and NH3 replacement both affect the observed (17)O-EDNMR signal envelope supporting the assignment of O5 as the exchangeable μ-oxo bridge and it acting as the first site of substrate inclusion.

Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N À Nb ond energy. Photochemical strategies that drive N 2 fixation are scarcely developed. Here,t he synthesis of ad inuclear N 2 -bridged complex is presented upon reduction of arhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2H + /2 e À transfer of the pincer ligand. Athreestep cycle is demonstrated for N 2 to nitrile fixation that relies on electrochemical reduction, photochemical N 2 -splitting and thermal nitrogen transfer. Figure 3. Left:CVof7 in presence of 0-15 equiv.b enzoic acid.Right: CV of 7 with 10 equiv 2,6-dichlorophenol under N 2 before CPE (orange), after 8hCPE at À1.65 V( pink) and after subsequent 5h CPE at À1.85 V(blue).Scheme 3. Optimized, three-steps ynthetic cycle. Angewandte ChemieCommunications 833

The Mn(IV)3CaO4 cubane is a structural motif present in the oxygen-evolving complex (OEC) of photosystem II and in water-oxidizing Mn/Ca layered oxides. This work investigates the magnetic and spectroscopic properties of two recently synthesized complexes and a series of idealized models that incorporate this structural unit. Magnetic interactions, accessible spin states, and (55)Mn isotropic hyperfine couplings are computed with quantum chemical methods and form the basis for structure-property correlations. Additionally, the effects of oxo-bridge protonation and one-electron reduction are examined. The calculated properties are found to be in excellent agreement with available experimental data. It is established that all synthetic and model Mn(IV)3CaO4 cubane complexes have the same high-spin S = (9)/2 ground state. The magnetic coupling conditions under which different ground spin states can be accessed are determined. Substitution of Mn(IV) magnetic centers by diamagnetic ions [e.g., Ge(IV)] allows one to "switch off" specific spin sites in order to examine the magnetic orbitals along individual Mn-Mn exchange pathways, which confirms the predominance of ferromagnetic interactions within the cubane framework. The span of the Heisenberg spin ladder is found to correlate inversely with the number of protonated oxo bridges. Energetic comparisons for protonated models show that the tris-μ-oxo bridge connecting only Mn ions in the cubane has the lowest proton affinity and that the average relaxation energy per additional proton is on the order of 18 kcal·mol(-1), thus making access to ground states other than the high-spin S = (9)/2 state in these cubanes unlikely. The relevance of these cubanes for the OEC and synthetic oxides is discussed.

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 is only this higher-spin form of the S2 state that progresses to the "activated" S3 state of the catalyst. The structure of this final metastable catalytic state was resolved in a recent report, showing that all manganese ions are six-coordinate. The magnetic coupling is dominantly ferromagnetic, leading to a high-spin ground state of SGS = 3. The ability of the Mn4O5Ca cofactor to adopt two distinct structural and spin-state forms in the S2 state is critical for water binding in the S3 state, allowing spin-state crossing from the inactive, low-spin configuration of the catalyst to the activated, high-spin configuration. Here we describe how an understanding of the magnetic properties of the catalyst in all S states has allowed conclusions on the catalyst function to be reached. A summary of recent literature results is provided that constrains the sequence of molecular level events: catalyst/substrate deprotonation, manganese oxidation, and water molecule insertion.

A systematic study of the magnetic coupling in homovalent (III-III and IV-IV) and heterovalent (III-IV) manganese dimers as a function of the chemical identity and coordination mode of the bridging ligands is carried out with the aim of establishing a reference library of magnetostructural correlations. Emphasis is placed on rationalising the results through analysis of the superexchange pathways in terms of corresponding orbitals. Additionally, the influence of specific structural distortions on magnetic properties is explored. Consistent with chemical intuition and decades of experience, oxo bridges are shown to be efficient mediators of superexchange, primarily through pi-type pathways, whereas the introduction of bridging carboxylates inhibits the magnetic coupling of the metal centres by introducing structural distortions in the core and by reducing the antiferromagnetic contribution to the exchange. Protonation of oxo bridges is shown to induce a predictably systematic reduction in the magnitude of antiferromagnetic coupling by switching off the dominant antiferromagnetic exchange pathways. In the case of weakly coupled dimers, this can even induce a reversal of the coupling from antiferromagnetic to ferromagnetic.