As inspired by the coordination environment of nickel in NikR and NiSOD, imidazole ligands were incorporated into N2SNiII square planar complexes in order to investigate the electronic and structural features of NiII species containing both imidazole and thiolate ligation. Rare examples of nickel complexes containing such ligand sets in continuous tetradentate (N2N'S) and discontinuous (N2S---N') coordination were synthesized and characterized. A significant finding in these studies is that the plane of the imidazole ligand is oriented perpendicular to the N2SNi plane. Further investigations addressed the orientational preference and stereodynamic nature of flat monodentate ligands (L = imidazoles, pyridine and an N-heterocyclic carbene) bound to planar N2SNi moieties. The solid state molecular structures of planar [N2SNiL]n+ complexes accessed through bridge-splitting reactions of dimeric, thiolate-S bridged [N2SNi]2 complexes, reveal that the plane of the added monodentate ligand orients largely orthogonal to the N2SNiL square plane. Variable temperature 1H NMR characterization of dynamic processes and ground state isomeric ratios of imidazole complexes in their stopped exchange limiting spectra, readily correlate with DFT-guided interpretation of Ni-L rotational activation barriers. Full DFT characterization relates the orientation mainly to steric hindrance derived both from ligand and binding pocket. In the case of the imidazole ligands a minor electronic contribution derives from intramolecular electrostatic interactions (imidazole C-2 C-H[superscript delta]+- - S[superscript delta]- interaction). Our group has firmly established the versatility of the (bme-daco)2-, (bme-dach)2-, and (ema)[left arrow]- ligands to accommodate a number of metals (M = Ni, Zn, Cu, and Fe ), and have demonstrated reactivity of such N2S2M complexes occurs predominately at the S-thiolate sites. As vanadium is of interest for its biological, pharmacological and spectroscopic/analytical probe abilities, vanadyl analogues were explored as mimics of possible chelates formed from Cys-X-Cys binding sites in vivo. The structural and electronic changes from the incorporation of V=O2+ in such dianionic and tetraanionic N2S2 binding pockets is investigated and compared to Ni2+ and Zn2+ in similar N2S2 environments. The nucleophilicity of the S-thiolate in these systems is explored with alkylating agents and W(CO)x. Furthermore, the vanadyl interaction with the CGC peptide, the biological analogue of the tetraanionic N2S2 ligand, was produced and characterized by EPR; its W(CO)x adducts were indentified by ?(CO) infrared spectroscopy.

Herein, a series of tin and oxidovanadium complexes, as well as a hexanuclear manganese cluster, supported by the bidentate, dianionic perfluoropinacolate (pinF) ligand, {(O(C(CF3)2)2}2−, are reported. While six-coordinate SnIV-pinF complexes (2.1−2.3) were found to be spectroscopically similar to SnO2 (cassiterite), four-coordinate SnII-pinF complexes (2.4−2.5) possess low 119Sn NMR chemical shifts and remarkably high quadrupolar splitting. Additionally, the Sn(II) complexes are unusually unreactive towards both Lewis acids and bases. Computational analysis suggests that this lack of reactivity with Lewis acids arises from the energetic inaccessibility of the HOMO (5s), and the lack of reactivity with Lewis bases is due to donation into the LUMO (5px) by fluorine atoms on the ligand. Furthermore, monomeric and dimeric {VIV=O}- and {VV=O}-pinF complexes (3.1−3.4) were synthesized and characterized, including (Me4N)2[V2(O)2(μ-O)2(pinF)2] (3.3a). Complex 3.3a was found to catalyze the oxidation of several benzyl alcohols at room-temperature under ambient conditions, reproducing reactivity known for VOx surfaces and demonstrating the thermodynamically challenging selective oxidation of alcohols to aldehydes/ketones. Finally, a hexanuclear manganese cluster, {MnIII4MnIV2(pinF)6(OK(THF))4(OH)4}, abbreviated {Mn6} (4.1) which contains four-fold axial symmetry, and its oxidized analog {MnIII3MnIV3(pinF)6(OK(THF))4(OH)4}[PF6] (4.2), were prepared and characterized. High-field EPR measurements of 4.1 confirm a high spin magnetic ground state of ST = 11, corroborating the oxidation state assignments of the manganese centers. While EPR and CTM data suggest the possibility of slow magnetic relaxation for 4.1, field-dependent SQUID magnetometry reveals a lack of magnetic hysteresis, precluding the SMM behavior hypothesized for 4.1.

The three-dimensional x-ray structure of 2,2'-bipyridylglycinatochloro copper(II) dihydrate has been fully refined to a final R factor of 0.081. The bipyridyl and glycine ligands are arranged about the central copper atom in a square planar configuration while the chlorine atom is 2.635 angstroms above this plane directly over the copper atom. This unusually long distance is explained by the positioning of a glycine group on the opposite side of the square plane, resulting in a distorted octahedral arrangement. Also, the chlorine atom is linked to three oxygen atoms via hydrogen bonding, thus stabilizing the distorted octahedral complex.

Der Großteil der Erdkruste besteht aus Metalloxiden, wobei Siliziumdioxid, Aluminiumoxid und Eisenoxide die Hauptbestandteile sind. Waren Metalloxide in der Menschheitsgeschichte zunächst hauptsächlich als Pigmente und als Rohstoffe zur Metallgewinnung interessant, so wuchs ihre Bedeutung mit wachsendem chemischem Wissen. Die Mechanismen der Bildung und des Zerfalls von Metalloxiden sind sehr komplex und bisher kaum verstanden. Genau dieses Wissen wird aber benötigt, um Metalloxide mit bestimmten Eigenschaften herzustellen und nutzen zu können. In dieser Arbeit werden daher einfache Silanole als molekulare Modelle für Silikate als Ligandvorläufer verwendet, um Eisensilanolatkomplexe zu synthetisieren. Die daraus erhaltenen Eisensilanolatkomplexe können als strukturelle Modelle für natürliche und synthetische Eisensilikate angesehen werden. Zur Aufklärung der Bildung von Eisensilikaten sowie der Struktur des aktiven Zentrums von eisenhaltigen Zeolithen werden diese Eisensilikate sowohl strukturell als auch spektroskopisch eingehend untersucht und mit den Ergebnissen von natürlichen und synthetischen Eisensilikaten verglichen. Die außergewöhnliche Kombination aus quadratisch planarer Koordination und high-spin Konfiguration der Eisen(II)ionen der in dieser Arbeit diskutierten entstehenden Komplexe entpuppt sich als charakteristisch für das aktive Zentrum von eisenhaltigen Zeolithen, weshalb die Eisensilanolatkomplexe in dieser Arbeit als gute strukturelle Modelle solcher angesehen werden können. / The main part of the earth’s crust consists of metal oxides with silica, alumina and iron oxide as major constituents. Metal oxides were used as pigments and as raw material for metal production, but with increasing chemical knowledge their importance grew. The mechanism of formation and decomposition is complex and still rarely understood. But this knowledge is needed, to synthesize and use metal oxides with distinct properties. In this work simple silanols as molecular models for silicates are used as ligand precursors to synthesize iron silanolate complexes. Those complexes can be considered as structural models for natural and synthetic iron silicates. To understand the mechanism of formation of iron silicates and also the structure of the active centre of iron containing zeolites, those iron complexes are analysed structurally and spectroscopically. The results are compared to those of natural and synthetic iron silicates. The extraordinary combination of square planar coordination and high-spin configuration of the iron(II) ion in the discussed iron complexes turns out to be characteristic for the active centre of iron containing zeolites, thus making the resulting complexes good structural models for the active centre of iron containing zeolites.

Les interactions entre des complexes de platine (II) ou de palladium (II) ont une grande influence sur une grande gamme de propriétés chimiques et physiques. Ces propriétés peuvent être étudiées par plusieurs méthodes spectroscopiques comme la spectroscopie Raman, d’absorption, d’émission et de réflectivité diffuse. L’empilement de molécules a un effet important sur les propriétés spectroscopiques de plusieurs composés des éléments de transition. La spectroscopie est très utile pour comprendre les effets intermoléculaires majeurs de plusieurs composés inorganiques. Les complexes plan-carré de platine(II) et de palladium(II) sont très intéressants à cause de leur grande quantité d’effets intermoléculaires et intramoléculaires. Des mesures avec des variations de pression (entre 1 bar et 40 kbar) et de température (entre 80 K et 300 K) ont été effectuées sur ces complexes. La structure à l’état fondamental des composés de platine(II) et de palladium(II) a un effet important sur la spectroscopie de luminescence. Des complexes avec des donneurs axiaux mènent à un effet de déplacement du maximum d’émission vers de plus basses énergies avec l’augmentation de pression. Des complexes similaires sans composante axiale ont un maximum d’émission qui se déplace vers des plus hautes énergies. Ces effets sont explorés à l’aide de plusieurs composés incluant une série de complexes pinceur qui ont démontré des déplacements entre -1 cm-1/kbar et -30 cm-1/kbar. Le changement du type d’émission causé par un changement de pression ou de température est aussi observable. Un complexe de platine(II) montre un changement d’une transition centrée sur le ligand à pression ambiante à une transition de type transfert de charge à plus haute pression. La combinaison de l’information cristallographique et spectroscopique donne de l’information quantitative sur les variations de la structure et des niveaux électroniques de plusieurs complexes. / Interactions between platinum(II) or palladium (II) compounds influence a large range of chemical and materials properties. These properties can be studied with the help of many different spectroscopic methods such as Raman, absorption, luminescence and diffuse reflectance. The stacking of molecules has a very important effect on their photophysical properties. Luminescence spectroscopy is especially useful to understand what role of intermolecular effects in inorganic complexes. Square planar Pt(II) and Pd(II) complexes are very interesting to study because of their multiple intermolecular and intramolecular effects. Work on these complexes under variable external pressure and temperature corresponding to variable intermolecular effects was executed. These changes include variations of pressure (between ambient pressure and 40 kbar) and temperature (from 80 K to 300 K). The ground-state structure of Pt(II) and Pd(II) square planar complexes has an obvious impact on the luminescence properties. Pressure allows a continuous variation of the structure. Complexes with axial donors show a shift of the luminescence maxima to lower energy as pressure increases, similar complexes without the axial component show a shift of the luminescence maxima to higher energy. The packing also plays an important role defining effects of pressure and temperature. These effects are illustrated with a series of pincer complexes that have shown energy shifts between -1 cm-1/kbar and -30 cm-1/kbar. These complexes also show different emitting states depending on the pressure that is applied. A ligand centered (LC) transition is observed at low pressure replaced by a metal-ligand charge transfer (MLCT) emission at higher pressure. The combination of crystallographic and spectroscopic data gives quantitative variations of the electronic structure for many complexes.

Phase Shifters are one of the most important building cells of the applications in microwave and millimeter-wave range, especially for communications and radar applications / to steer the main beam for electronic scanning. This thesis includes all of the stages starting from the theoretical design stage to the measurements of the phase shifters. In detail, all-pass network phase shifter configuration is used to achieve broadband and ultra wide-band differential phase characteristics. For these reasons, 1 to 2 GHz, 2 to 4 GHz, and 3 to 6 GHz 4-bit, 22.5&deg / phase resolution phase shifter realization with surface micromachined lumped components are designed, simulated, fabricated and measured. Basic building blocks of the phase shifters, i.e., surface micromachined lumped components, square planar spiral inductors and Metal-Insulator-Metal capacitors are designed with EM simulation and lumped equivalent model extractions. The validation of the designed square planar spiral inductors is done with fabrication and measurement steps, very low error, below 1%, between the designs and fabricated samples are observed. Using this knowledge on lumped elements finally phase shifters are designed with surface micromachined lumped components, fabricated using an in house technology provided by METU-MEMS facilities, RF MEMS group. Low phase rms error, good return and insertion loss considerations are aimed, and achieved. In addition to the main work of this thesis, a generalized theoretical calculation method for 2n-1 number of stages all-pass network phase shifters is presented for the first time in literature. A different, new, broadband, and combined phase shifter topology using two-stage all-pass filters is presented. Moreover, the implementation of this idea is proved to be practical to 3 to 6 GHz 5.625&deg / and 11.25&deg / combined phase shifter. A new approach for stage numbers other than power of 2 is indicated, which is different from what is already presented in the literature. An example practical implementation results are provided for the three-stage 4-bit 1 to 6 GHz phase shifter. Also, a small improvement in SRF of the high inductance valued inductors is achieved with the mitering of the corners of square planar spiral inductors. Comparison of the measured data between the normal inductors and mitered versions shows that the first SRF of the inductors are increased about 80 MHz, and second SRF of the inductors are increased about 200 MHz.

Les interactions entre des complexes de platine (II) ou de palladium (II) ont une grande influence sur une grande gamme de propriétés chimiques et physiques. Ces propriétés peuvent être étudiées par plusieurs méthodes spectroscopiques comme la spectroscopie Raman, d’absorption, d’émission et de réflectivité diffuse. L’empilement de molécules a un effet important sur les propriétés spectroscopiques de plusieurs composés des éléments de transition. La spectroscopie est très utile pour comprendre les effets intermoléculaires majeurs de plusieurs composés inorganiques. Les complexes plan-carré de platine(II) et de palladium(II) sont très intéressants à cause de leur grande quantité d’effets intermoléculaires et intramoléculaires. Des mesures avec des variations de pression (entre 1 bar et 40 kbar) et de température (entre 80 K et 300 K) ont été effectuées sur ces complexes. La structure à l’état fondamental des composés de platine(II) et de palladium(II) a un effet important sur la spectroscopie de luminescence. Des complexes avec des donneurs axiaux mènent à un effet de déplacement du maximum d’émission vers de plus basses énergies avec l’augmentation de pression. Des complexes similaires sans composante axiale ont un maximum d’émission qui se déplace vers des plus hautes énergies. Ces effets sont explorés à l’aide de plusieurs composés incluant une série de complexes pinceur qui ont démontré des déplacements entre -1 cm-1/kbar et -30 cm-1/kbar. Le changement du type d’émission causé par un changement de pression ou de température est aussi observable. Un complexe de platine(II) montre un changement d’une transition centrée sur le ligand à pression ambiante à une transition de type transfert de charge à plus haute pression. La combinaison de l’information cristallographique et spectroscopique donne de l’information quantitative sur les variations de la structure et des niveaux électroniques de plusieurs complexes. / Interactions between platinum(II) or palladium (II) compounds influence a large range of chemical and materials properties. These properties can be studied with the help of many different spectroscopic methods such as Raman, absorption, luminescence and diffuse reflectance. The stacking of molecules has a very important effect on their photophysical properties. Luminescence spectroscopy is especially useful to understand what role of intermolecular effects in inorganic complexes. Square planar Pt(II) and Pd(II) complexes are very interesting to study because of their multiple intermolecular and intramolecular effects. Work on these complexes under variable external pressure and temperature corresponding to variable intermolecular effects was executed. These changes include variations of pressure (between ambient pressure and 40 kbar) and temperature (from 80 K to 300 K). The ground-state structure of Pt(II) and Pd(II) square planar complexes has an obvious impact on the luminescence properties. Pressure allows a continuous variation of the structure. Complexes with axial donors show a shift of the luminescence maxima to lower energy as pressure increases, similar complexes without the axial component show a shift of the luminescence maxima to higher energy. The packing also plays an important role defining effects of pressure and temperature. These effects are illustrated with a series of pincer complexes that have shown energy shifts between -1 cm-1/kbar and -30 cm-1/kbar. These complexes also show different emitting states depending on the pressure that is applied. A ligand centered (LC) transition is observed at low pressure replaced by a metal-ligand charge transfer (MLCT) emission at higher pressure. The combination of crystallographic and spectroscopic data gives quantitative variations of the electronic structure for many complexes.

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