Raman Spectroscopy of Oxygen Evolution Catalysts and PSII Manganese Model Compounds

Photosynthesis is the basis of life on earth, and oxygen evolution catalysts are key components of this complicated, yet not fully understood process. Photosystem II, a large membrane bound pigment-protein complex, is the key system that facilitates oxygenic photosynthesis via the oxygen evolving complex (a natural oxygen evolving catalyst). It is a key component in oxygen producing catalysts, which can be used in fields such as energy production and biomimetic catalysts. The oxygen evolution cycle, or Kok cycle going within it is still not studied completely. In this project, we were studying the vibrational (and structural) state of a Manganese model compound for PSII and functioning Ruthenium water oxidizing catalyst. The method for this experiment was Raman spectroscopy at two wavelengths in the visible region: 532nm and 442nm. The results obtained from our Manganese model compound are various Raman spectra which will be analyzed using DFT (Density Function theory) and can now be used to predict vibrations relevant to PSII while insights gained from functioning Ruthenium water oxidizing catalysts give clues to the chemistry of PSII

Mechanism of Catalytic Water Oxidation by the Ruthenium Blue Dimer Catalyst: Comparative Study in D2O versus H2O

Water oxidation is critically important for the development of energy solutions based on the concept of artificial photosynthesis. In order to gain deeper insight into the mechanism of water oxidation, the catalytic cycle for the first designed water oxidation catalyst, cis,cis-[(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ (bpy is 2,2-bipyridine) known as the blue dimer (BD), is monitored in D2O by combined application of stopped flow UV-Vis, electron paramagnetic resonance (EPR) and resonance Raman spectroscopy on freeze quenched samples. The results of these studies show that the rate of formation of BD[4,5] by Ce(IV) oxidation of BD[3,4] (numbers in square bracket denote oxidation states of the ruthenium (Ru) centers) in 0.1 M HNO3, as well as further oxidation of BD[4,5] are slower in D2O by 2.1–2.5. Ce(IV) oxidation of BD[4,5] and reaction with H2O result in formation of an intermediate, BD[3,4]′, which builds up in reaction mixtures on the minute time scale. Combined results under the conditions of these experiments at pH 1 indicate that oxidation of BD[3,4]′ is a rate limiting step in water oxidation with the BD catalyst

Visible Light-Induced Electron Transfer from Di-mu-oxo Bridged Dinuclear Mn Complexes to Cr Centers in Silica Nanopores

The compound (bpy)2MnIII(mu-O)2MnIV(bpy)2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single CrVI charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of MnIII(mu-O)2MnIV demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of CrVI centers. The FT-Raman spectrum upon visible light excitation of the CrVI-OII --> CrV-OI ligand-to-metal charge-transfer reveals electron transfer from MnIII(mu-O)2MnIV (Mn-O stretch at 700 cm-1) to CrVI, resulting in the formation of CrV and MnIV(mu-O)2MnIV (Mn-O stretch at 645 cm-1). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (DELTA Eo = -0.6 V) remain after several minutes, which points to spatial separation of CrV and MnIV(mu-O)2MnIV as a consequence of hole (OI) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well defined transition metal molecular units, with the ultimate goal of performing endothermic, multi-electron transformations that are coupled to visible light electron pumps in nanostructured scaffolds

Electronic Structure and Oxidation State Changes in the Mn4Ca Cluster of Photosystem II

Oxygen-evolving complex (Mn4Ca cluster) of Photosystem II cycles through five intermediate states (Si-states, i =0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn4(III2,IV2) and Mn4(III,IV3) for S1 and S2 states, while it is still controversial for the S0 and S3 states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn4Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra (metal spin state) simultaneously. We have collected data from PSII samples in the each of the S-states and compared them with data from various inorganic Mncomplexes. The spectral changes in the Mn 1s2p3/2 RIXS spectra between the S-states were compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S0 to S1, and S1 to S2 transitions is twice as large as that during the S2 to S3 transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms

Where Water is Oxidized to Dioxygen: Structure of thePhotosynthetic Mn4Ca Cluster

Oxidation of water to dioxygen is catalyzed withinphotosystem II (PSII) by a Mn4Ca cluster, the structure of which remainselusive. Polarized extended X-ray absorption fine structure (EXAFS)measurements on PSII single crystals constrain the Mn4Ca cluster geometryto a set of three similar high-resolution structures. Combining polarizedEXAFS and X-ray diffraction data, the cluster was placed within PSIItaking into account the overall trend of the electron density of themetal site and the putative ligands. The structure of the cluster fromthe present study is unlike either the 3.0 or 3.5 Angstrom resolutionX-ray structures, and other previously proposed models