Magnus F. Anderlund

Biomimetic and Microbial Approaches to Solar Fuel Generation

Photosynthesis is performed by a multitude of organisms, but in nearly all cases, it is variations on a common theme: absorption of light followed by energy transfer to a reaction center where charge separation takes place. This initial form of chemical energy is stabilized by the biosynthesis of carbohydrates. To produce these energy-rich products, a substrate is needed that feeds in reductive equivalents. When photosynthetic microorganisms learned to use water as a substrate some 2 billion years ago, a fundamental barrier against unlimited use of solar energy was overcome. The possibility of solar energy use has inspired researchers to construct artificial photosynthetic systems that show analogy to parts of the intricate molecular machinery of photosynthesis. Recent years have seen a reorientation of efforts toward creating integrated light-to-fuel systems that can use solar energy for direct synthesis of energy-rich compounds, so-called solar fuels. Sustainable production of solar fuels is a long awaited development that promises extensive solar energy use combined with long-term storage. The stoichiometry of water splitting into molecular oxygen, protons, and electrons is deceptively simple; achieving it by chemical catalysis has proven remarkably difficult. The reaction center Photosystem II couples light-induced charge separation to an efficient molecular water-splitting catalyst, a Mn(4)Ca complex, and is thus an important template for biomimetic chemistry. In our aims to design biomimetic manganese complexes for light-driven water oxidation, we link photosensitizers and charge-separation motifs to potential catalysts in supramolecular assemblies. In photosynthesis, production of carbohydrates demands the delivery of multiple reducing equivalents to CO(2). In contrast, the two-electron reduction of protons to molecular hydrogen is much less demanding. Virtually all microorganisms have enzymes called hydrogenases that convert protons to hydrogen, many of them with good catalytic efficiency. The catalytic sites of hydrogenases are now the center of attention of biomimetic efforts, providing prospects for catalytic hydrogen production with inexpensive metals. Thus, we might complete the water-to-fuel conversion: light + 2H(2)O --> 2H(2) + O(2). This reaction formula is to some extent already elegantly fulfilled by cyanobacteria and green algae, water-splitting photosynthetic microorganisms that under certain conditions also can produce hydrogen. An alternative route to hydrogen from solar energy is therefore to engineer these organisms to produce hydrogen more efficiently. This Account describes our original approach to combine research in these two fields: mimicking structural and functional principles of both Photosystem II and hydrogenases by synthetic chemistry and engineering cyanobacteria to become better hydrogen producers and ultimately developing new routes toward synthetic biology.

Photochemical water oxidation with visible light using a cobalt containing catalyst

Artificial photosynthesis aims at using solar light energy to oxidatively split water to oxygen, protons and electrons and store the energy in a chemical fuel. Here we present a cobalt phosphonate material that can split water catalytically, driven by visible light in aqueous solutions of pH 7.

Two tetranuclear Mn-complexes as biomimetic models of the oxygen evolving complex in Photosystem II. A synthesis, characterisation and reactivity study

In this work we report the preparation of two metallamacrocyclic tetranuclear manganese(II) complexes, [L1(4)Mn4](ClO4)4 and [L2(4)Mn4](ClO4)4 where L1 and L2 are the anions of the heptadentate ligands 2-((2-(bis(pyridin-2-ylmethyl)amino)ethyl)(methyl)amino)acetic acid and 2-(benzyl(2-(bis(pyridin-2-ylmethyl)amino)ethyl)amino)acetic acid), respectively. The complexes have been fully characterized by ESI-MS, elemental analysis, single-crystal X-ray diffraction, magnetic susceptibility, and EPR spectroscopy. Electrochemical reactions as well as reactions with different chemical redox reagents have been performed and a reversible two electron oxidation per manganese ion has been identified. The reaction of [L1(4)Mn4](ClO4)4 with oxone or cerium(IV) results in the evolution of oxygen which makes this system interesting for future studies in the search for a functional mimic of the oxygen evolving complex in Photosystem II.

Water oxidation by manganese oxides formed from tetranuclear precursor complexes: the influence of phosphate on structure and activity

Two types of manganese oxides have been prepared by hydrolysis of tetranuclear Mn(iii) complexes in the presence or absence of phosphate ions. The oxides have been characterized structurally using X-ray absorption spectroscopy and functionally by O2 evolution measurements. The structures of the oxides prepared in the absence of phosphate are dominated by di-μ-oxo bridged manganese ions that form layers with limited long-range order, consisting of edge-sharing MnO6 octahedra. The average manganese oxidation state is +3.5. The structure of these oxides is closely related to other manganese oxides reported as water oxidation catalysts. They show high oxygen evolution activity in a light-driven system containing [Ru(bpy)3](2+) and S2O8(2-) at pH 7. In contrast, the oxides formed by hydrolysis in the presence of phosphate ions contain almost no di-μ-oxo bridged manganese ions. Instead the phosphate groups are acting as bridges between the manganese ions. The average oxidation state of manganese ions is +3. This type of oxide has much lower water oxidation activity in the light-driven system. Correlations between different structural motifs and the function as a water oxidation catalyst are discussed and the lower activity in the phosphate containing oxide is linked to the absence of protonable di-μ-oxo bridges.

Mechanistic studies on the water-oxidizing reaction of homogeneous manganese-based catalysts: isolation and characterization of a suggested catalytic intermediate.

The synthesis, isolation, and characterization of two high-valent manganese dimers with isomeric ligands are reported. The complexes are synthesized and crystallized from solutions of low-valent precursors exposed to tert-butyl hydroperoxide. The crystal structures display centrosymmetric complexes consisting of Mn(2)(IV,IV)(μ-O)(2) cores, with one ligand coordinating to each manganese. The ligands coordinate with the diaminoethane backbone, the carboxylate, and one of the two pyridines, while the second pyridine is noncoordinating. The activity of these complexes, under water oxidation conditions, is discussed in light of a proposed mechanism for water oxidation, in which this type of complexes have been suggested as a key intermediate.

First turnover analysis of water-oxidation catalyzed by Co-oxide nanoparticles

Co-oxides are promising water oxidation catalysts for artificial photosynthesis devices. Presently, several different proposals exist for how they catalyze O-2 formation from water. Knowledge about ...

Room-Temperature Energy-Sampling Kβ X-ray Emission Spectroscopy of the Mn4Ca Complex of Photosynthesis Reveals Three Manganese-Centered Oxidation Steps and Suggests a Coordination Change Prior to O2 Formation.

In oxygenic photosynthesis, water is oxidized and dioxygen is produced at a Mn4Ca complex bound to the proteins of photosystem II (PSII). Valence and coordination changes in its catalytic S-state cycle are of great interest. In room-temperature (in situ) experiments, time-resolved energy-sampling X-ray emission spectroscopy of the Mn Kβ1,3 line after laser-flash excitation of PSII membrane particles was applied to characterize the redox transitions in the S-state cycle. The Kβ1,3 line energies suggest a high-valence configuration of the Mn4Ca complex with Mn(III)3Mn(IV) in S0, Mn(III)2Mn(IV)2 in S1, Mn(III)Mn(IV)3 in S2, and Mn(IV)4 in S3 and, thus, manganese oxidation in each of the three accessible oxidizing transitions of the water-oxidizing complex. There are no indications of formation of a ligand radical, thus rendering partial water oxidation before reaching the S4 state unlikely. The difference spectra of both manganese Kβ1,3 emission and K-edge X-ray absorption display different shapes for Mn(III) oxidation in the S2 → S3 transition when compared to Mn(III) oxidation in the S1 → S2 transition. Comparison to spectra of manganese compounds with known structures and oxidation states and varying metal coordination environments suggests a change in the manganese ligand environment in the S2 → S3 transition, which could be oxidation of five-coordinated Mn(III) to six-coordinated Mn(IV). Conceivable options for the rearrangement of (substrate) water species and metal-ligand bonding patterns at the Mn4Ca complex in the S2 → S3 transition are discussed.

Towards a comprehensive X-ray approach for studying the photosynthetic manganese complex–XANES, Kα/Kβ/Kβ-satellite emission lines, RIXS, and comparative computational approaches for selected model complexes

Advanced X-ray spectroscopy experiments can contribute to elucidation of the mechanism of water oxidation in biological (tetra-manganese complex of Photosystem II) and artificial systems. Although the electronic structure of the catalytic metal site is of high interest, it is experimentally not easily accessible. Therefore, we and other researchers are working towards a comprehensive approach involving a combination of methods, namely (1) quantitative analysis of X-ray absorption near-edge structure (XANES) spectra collected at the K-edge and, in the long run, at the L-edge of manganese; (2) high-resolution X-ray emission spectroscopy (XES) of Kα and Kβ lines, (3) two-dimensional resonant inelastic X-ray scattering (RIXS) spectra. Collection of these spectroscopic data sets requires state-of-the-art synchrotron radiation facilities as well as experimental strategies to minimize the radiation-induced modifications of the samples. Data analysis requires the use and development of appropriate theoretical tools. Here, we present exemplary data collected for three multi-nuclear synthetic Mn complexes with the Mn ions in the oxidation states II, III, and IV, and for MnVII of the permanganate ion. Emission spectra are calculated for the MnVII ion using both multiple-scattering (MS) approach and time-dependent density functional theory (TDDFT).

FTIR Study of Manganese Dimers with Carboxylate Donors As Model Complexes for the Water Oxidation Complex in Photosystem II

The carboxylate stretching frequencies of two high-valent, di-μ-oxido bridged, manganese dimers has been studied with IR spectroscopy in three different oxidation states. Both complexes contain one monodentate carboxylate donor to each Mn ion, in one complex, the carboxylate is coordinated perpendicular to the Mn-(μ-O)(2)-Mn plane, and in the other complex, the carboxylate is coordinated in the Mn-(μ-O)(2)-Mn plane. For both complexes, the difference between the asymmetric and the symmetric carboxylate stretching frequencies decrease for both the Mn(2)(IV,IV) to Mn(2)(III,IV) transition and the Mn(2)(III,IV) to Mn(2)(III,III) transition, with only minor differences observed between the two arrangements of the carboxylate ligand versus the Mn-(μ-O)(2)-Mn plane. The IR spectra also show that both carboxylate ligands are affected for each one electron reduction, i.e., the stretching frequency of the carboxylate coordinated to the Mn ion that is not reduced also shifts. These results are discussed in relation to FTIR studies of changes in carboxylate stretching frequencies in a one electron oxidation step of the water oxidation complex in Photosystem II.

Tetraethylammonium [12,12‐diethyl‐2,2,9,9‐tetramethyl‐1,4,7,10‐tetraza‐5,6‐benzotridecane‐3,8,11,13‐tetraone(4−)]oxidomanganate(V)

The Mn-V complex in the title compound, (C8H20N)[ Mn(C21H26N4O4)O], is interesting as it has been suggested that Mn-V oxospecies are intermediates both in epoxidation of alkenes and in water oxidat ...