<p>This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II.</p><p>The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown.</p><p>One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D^––P–A⁺) showed an unusual long lifetime for triad based on ruthenium photosensitizers.</p><p>The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.</p>

<p>In natural oxygen-producing photosynthesis solar energy is stored as chemical energy, in carbohydrates, fats and amino acids, using water as electron source. The large transmembrane protein complex, PSII, is the key enzyme in the light-driven reactions. Water oxidation is accomplished by a triad in PSII in which the Mn-cluster plays an important role. In the artificial photosynthetic system, nature’s photosynthesis will be mimicked such that hydrogen, a sustainable energy source, can be produced from solar energy and water alone. Since water oxidiation requires the catalytic activity of a Mn-cluster in photosynthesis, different artificially constructed manganese complexes are investigated. </p><p>The dinuclear ([Mn₂(II,III)L(µ-OAc)₂]ClO₄), where L is the X-anion of 2-(<i>N,N</i>-Bis(2-methylpyridyl)aminomethyl)-6-(<i>N</i>-(3,5-ditert-butylbenzyl-2-hydroxy)-<i>N</i>-(pyridylmethyl)aminomethyl)-4-methylphenol, an unsymmetric ligand with two coordinating phenolate groups, has been studied. The two Mn-ions are linked via a mono-µ-oxo bridge and two acetate ligands. Q-band Electron Paramagnetic Resonance was conducted on the Unsymmetric Mn₂(II,III) Complex. Aquired results show that the complex has a 2600 Gauss broad signal (11 400-14 000 Gauss) with 14-17 lines at g~2 and hyperfines of 120 Gauss. This is consistent with previous X-band studies. Q-band spectra of the Unsymmetric Mn(II,III) display increased hyperfine resolution compared to Qband spectra of the symmetric complex, Mn₂(bpmp)(µ-OAC)₂. This is noticeable since Unsymmetric Mn2(II,III) and Mn₂ (bpmp)(µ-OAC)₂ partly overlap in low-frequency experiments (X-band EPR). </p><p>Further investigations are yet to be expected. Nevertheless, the conducted thesis study provides important knowledge in the futuristic goal of building an artificial super-complex.</p>

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: George W. Luther, III., College of Marine and Earth Studies. Includes bibliographical references.

Thesis (doctoral)--Swedish University of Agricultural Sciences, 2004. / Thesis documentation sheet inserted. Errata sheet inserted. Appendix reprints four papers and manuscripts co-authored with others. Includes bibliographical references. Also issued electronically via World Wide Web in PDF format; online version lacks appendix.

This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II. The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown. One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D––P–A+) showed an unusual long lifetime for triad based on ruthenium photosensitizers. The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.

This dissertation is written in two parts. The first pertains to polycarbonate and polyester synthesis using relatively benign processes. The synthesis of polycarbonates from the coupling of CO2 and epoxides catalyzed by transition metal catalysts has long been studied in the DJD group. The benefits of this process are that it utilizes comparatively benign reagents, can be performed using no extraneous solvent, and is 100% atom efficient. A method potentially useful for achieving more desirable polycarbonate properties is to produce an epoxide A/epoxide B/CO2 terpolymer, thus allowing more fine "tuning" of properties to what one may desire while simultaneously influencing relative epoxide reactivity to potentially increase catalytic turnovers. Specifically, the coupling of propylene oxide and cyclohexene oxide with CO2 to yield a random copolymer with tunable properties has been studied via a Fineman-Ross analysis. Propylene oxide was found to be incorporated into the resultant polymer chain with anywhere from 4-10 times the preference of cylcohexene oxide. Although it has been reported as early as 1969, the copolymerization of epoxides and cyclic anhydrides catalyzed by transition metal complexes to yield polyesters via a chain-growth mechanism has recently gained much attention. This robust method of polyester synthesis can utilize rather inexpensive reagents to synthesize an array of polyester products which have a wide range of Tg values (-30 degrees C ? 90 degreesC), achievable through simple monomer selection. The second part of this dissertation deals with the kinetic study of ligand substitution from manganese carbonyl metal fragments. Some time ago it was postulated that complexes of the (Cp)M(CO)2L variety undergo ligand substitution via a associative mechanism allowed by a haptotropic eta5-eta3 shift in the eta5 ligand. Through kinetic studies and theoretical modeling, an approximate activation energy barrier of ~34 kJ/mol has been calculated for the ring slip of (2,5-dimethylpyrrole)Mn to occur. Additionally, further kinetic studies were performed in which Tp, a ligand electronically similar to Cp, was compared to MnCp complexes.

The development of efficient catalyst for water oxidation is of paramount importance to artificial photosynthesis, but before this can be achieved a deeper understanding of this reaction is essential. In nature this reaction occurs in a tetranuclear Mn-cluster which serves as the work-horse of oxygenic photosynthesis. This thesis summarises my efforts at developing molecular systems capable of mimicking this complex employing a biomimetic approach. Three different approaches towards this goal are described here-in. The first section describes a screening study, in which a number of manganese complexes were tested to see whether or not they were capable of catalysing the formation of dioxygen when treated with different oxidants (Papers I). For those reactions in which dioxygen formation was observed the reactions were repeated in labelled water and the incorporation of labelled O-atoms was studied by mass spectrometry. This allowed us to determine to what extent water was the source of the evolved dioxygen (Papers II-III). In Chapter three a reported catalyst and a derivative thereof is studied in depth. The influence of changes to the ligand on the oxygen–oxygen bond forming reaction could unfortunately not be reliably addressed, because of the instability of the complexes under “catalytic” conditions. Nevertheless, the study allowed us to revise the “carboxylate shift”-mechanism suggested in the literature (Papers IV-V). Chapter four describes the continuation of my work on ligands featuring the carboxylate ligand motif first introduced in Chapter three. In this study ligands containing multiple binding pockets were designed and synthesised (Paper VI). A better understanding of the mechanism in the natural water oxidising enzyme will facilitate the design of biomimetic complexes, this is discussed in Chapter five. In this work model complexes (Paper VII) are used to study the mechanism by which natures own water oxidising catalyst performs this reaction.

In natural oxygen-producing photosynthesis solar energy is stored as chemical energy, in carbohydrates, fats and amino acids, using water as electron source. The large transmembrane protein complex, PSII, is the key enzyme in the light-driven reactions. Water oxidation is accomplished by a triad in PSII in which the Mn-cluster plays an important role. In the artificial photosynthetic system, nature’s photosynthesis will be mimicked such that hydrogen, a sustainable energy source, can be produced from solar energy and water alone. Since water oxidiation requires the catalytic activity of a Mn-cluster in photosynthesis, different artificially constructed manganese complexes are investigated. The dinuclear ([Mn2(II,III)L(µ-OAc)2]ClO4), where L is the X-anion of 2-(N,N-Bis(2-methylpyridyl)aminomethyl)-6-(N-(3,5-ditert-butylbenzyl-2-hydroxy)-N-(pyridylmethyl)aminomethyl)-4-methylphenol, an unsymmetric ligand with two coordinating phenolate groups, has been studied. The two Mn-ions are linked via a mono-µ-oxo bridge and two acetate ligands. Q-band Electron Paramagnetic Resonance was conducted on the Unsymmetric Mn2(II,III) Complex. Aquired results show that the complex has a 2600 Gauss broad signal (11 400-14 000 Gauss) with 14-17 lines at g~2 and hyperfines of 120 Gauss. This is consistent with previous X-band studies. Q-band spectra of the Unsymmetric Mn(II,III) display increased hyperfine resolution compared to Qband spectra of the symmetric complex, Mn2(bpmp)(µ-OAC)2. This is noticeable since Unsymmetric Mn2(II,III) and Mn2 (bpmp)(µ-OAC)2 partly overlap in low-frequency experiments (X-band EPR). Further investigations are yet to be expected. Nevertheless, the conducted thesis study provides important knowledge in the futuristic goal of building an artificial super-complex.

The purpose of the study is to find a suitable method for removal of iron and manganese considering local economic and environmental aspects. El Salvador is situated in Central America with a coast line towards the Pacific Ocean. The country borders Guatemala and Honduras. Aguilares is a town situated in the department of San Salvador, with a population of approximately 33,000 people. Currently, the population is provided with water for about two hours per day, since it is the highest capacity of the existing wells. During these two hours many households fill a small tank with water to use for the remainder of the day. The water is not safe to use for oral consumption because of the levels of bacteria and other contamination. One of the wells, situated in the community of Florída is not in use at this date because of the high levels of Iron and Manganese in the ground water which cannot be removed with the present technique.Ground water is naturally pure from bacteria at a depth of 30 m or more, however solved metals may occur and if the levels are too high the water is unsuitable to drink. The recommended maximum levels by WHO (2008) [1] for Iron and Manganese are 2 mg/l and 0.5 mg/l respectively.Literature and field studies led to the following results; Iron and manganese can be removed by precipitation followed by separation. Precipitation is achieved by aeration, oxygenation or chemical oxidation and separation is achieved by filtration or sedimentation.The different methods all have advantages and disadvantages. However the conclusion reached in this report is that aeration and filtration should be used in the case of Florída. What equipment and construction that should be used depends on economic and resource factors as well as water requirements, which is up to the council of Aguilares to deliberate.

Excepting agricultural based products, which themselves require a great deal of energy to produce, our supply of natural resources such as minerals, metal ore, fresh water, coal, oil and natural gas are all limited in supply. The depletion of these substances is imminent and this knowledge weighs heavily on humankind. The utilization of CO2 for the production of polycarbonates is one attempt at exploiting a profoundly abundant and renewable resource. The importance of research in this and similar fields justifies the detailed study of the chemicals and procedures involved with this chemistry. This current work concentrates on the fundamental study of transition metal Schiff base complexes that have shown a great deal of promise in their ability to catalyze the copolymerization of CO2 and epoxide to form aliphatic polycarbonates. A new chromium(III) Schiff base complex has been synthesized and evaluated for its ability to catalyze the formation of polymer. The ligand employed bears an N2O2 coordination sphere identical to the widely utilized chromium(III) and cobalt(III) salen catalysts. This complex was shown to be active towards the copolymerization of CO2 and cyclohexene oxide. Although the activity was less than that seen with chromium(III) salen complex, the study demonstrates that new ligand systems are available beyond salen and deserve further attention. A class of manganese(III) Schiff base complexes was also synthesized and evaluated as catalysts. Although crystallographic data has shown that these complexes are structural analogs to chromium(III) salens, the difference in metal center leads to a nearly complete elimination of catalytic activity. Such a marked difference has been taken advantage of by using this very low activity to study the ring-opening of epoxide in the initial step of the copolymerization both mechanistically and kinetically. It has also been utilized in an evaluation of the coordination chemistry of the polymerization process. This has led to some valuable conclusions about the nature and role of the metal center that previously have not been studied. Manganese(III) salen complexes were also synthesized and evaluated in an effort to compare these important ligands to other Schiff bases and confirm the findings mentioned above.