Universiẗat, Diss., 2003--Tübingen.

Im Rahmen dieser Arbeit konnten, ausgehend von Borat-haltigen Salzen und ionischen Flüssigkeiten (ILs) sowie Lanthanid-haltigen Precursoren, 30 neue Komplexe und Koordinationspolymere dargestellt werden. Dazu wurden vielfältige Synthesestrategien verfolgt und angewendet, unter anderem Salzmetathesen in Lösung, Solvothermalsynthesen und Ionothermalsynthesen. Ein Hauptaugenmerk bei der Synthese der Zielverbindungen lag auf deren Eigenschaften, wobei insbesondere die Photolumineszenzeigenschaften der erhaltenen Koordinationsverbindungen untersucht wurden. Als Borat-haltige Liganden wurden sowohl Cyanoborate als auch Oxoborate hinsichtlich ihrer Eignung zum Aufbau neuer Koordinationspolymere untersucht. Als Cyanoborat-haltige Edukte wurden dabei Säuren und ionische Flüssigkeiten mit Dicyano-, Tricyano- und Tetracyanoborat- Anionen eingesetzt, die durch die unterschiedliche Zahl an Cyanogruppen zu vielfältigen Koordinationsverbindungen führen können. Mittels Ionothermalsynthese konnten die Verbindungen 1∞[Ln(NO3)2{B(CN)4}(H2O)4] (Ln = La, Eu) sowie [EMIm]1∞[LaNO3{B(CN)4}3(H2O)3] dargestellt werden, wobei es zu einer Transformation der ionischen Flüssigkeit [EMIm][B(CN)4] in ein Koordinationspolymer kommt, in dem sowohl Kation als auch Anion der IL beteiligt sind. Dabei ist es bemerkenswerterweise durch die Reaktionstemperatur möglich zu steuern, welches Produkt sich letztlich bildet. Ebenfalls durch Ionothermalsynthese gelang die Synthese von Einkristallen der Verbindung 3∞[La{C2F5B(CN)3}3], durch deren Kenntnis die Verbindungen 3∞[Ln{C2F5B(CN)3}3](Ln = Eu, Ho) als isotype Strukturen identifiziert und hinsichtlich ihrer Lumineszenzeigenschaften charakterisiert werden konnten. Durch Umsetzungen der Lanthanidchloride mit der Säure H[BH2(CN)2] in Solvothermalsynthesen in Pyridin (py) konnten eindimensionale Koordinationspolymere [H(py)2]1∞[LnCl2{BH2(CN)2}2(py)2]·0.5py (Ln = Ce, Pr) erhalten werden. Unter vergleichbaren Synthesebedingungen aber im Lösungsmittel MeCN beobachtet man hingegen die Bildung von Raumnetzen der Zusammensetzung 3∞[Ln2{BH2(CN)2}9]·[Ln(CH3CN)9] (Ln = Ce, Eu, Tb). Die dreidimensionalen Koordinationspolymere 3∞[Ln{BH(CN)3}3] (Ln = Eu, Tb) wurden ebenfalls in MeCN synthetisiert, allerdings ausgehend von der Säure [H3O][BH(CN)3]. Die erwähnten Verbindungen zeigen für die spektroskopisch relevanten Vertreter charakteristische Lumineszenz auf Basis von 5d-4f- respektive 4f-4f-Übergängen, die überwiegend auf der direkten Anregung der jeweiligen Lanthanidionen beruht. Mit dem Bis-salicylatoborat-Anion (= BSB−) gelang ausgehend von Na[BSB] und LnCl3 unter solvothermalen Bedingungen in Pyridin die Synthese der eindimensionalen, strangartigen Koordinationspolymere 1∞[Ln(BSB)3(py)2] (Ln = Y, La – Nd, Sm) und der zweidimensionalen, schichtartigen Verbindungen 2∞[Ln(BSB)3(py)] (Ln = Sm, Eu, Tb – Er). Einblicke über den Mechanismus der Bildung der genannten Verbindungen konnten durch den Komplex [ErCl2(py)4BSB] gewonnen werden, der eine sukzessive Substitution der Chlorid-Liganden nachweist. Die Verbindungen mit dem [BSB]−-Anion zeigen Photolumineszenz, die auf unterschiedliche Prozesse zurückgeführt werden kann. So weist 1∞[Y(BSB)3(py)2] Fluoreszenz auf, die von den [BSB]−-Anionen herrührt, während 1∞[Ln(BSB)3(py)2] (Ln = Ce, Nd, Sm) sowie 2∞[Ln(BSB)3(py)] (Ln = Sm, Tb, Dy) Lumineszenz auf Basis von 5d-4f- und 4f-4f-Übergängen zeigen, die durch einen Antenneneffekt der koordinierenden [BSB]−-Anionen vergleichsweise intensiv beobachtet werden können. Eine Sonderstellung nehmen hier die Verbindungen 2∞[Ln(BSB)3(py)] (Ln = Eu, Ho) ein. Während mit Eu3+ überwiegend direkte Anregung festgestellt werden kann, treten für Ho3+ Reabsorptionsprozesse auf. Durch Kombination unterschiedlicher Gehalte an Eu3+- bzw. Tb3+-Ionen in den eindimensionalen Koordinationspolymeren 1∞[EuxTb1−x(BSB)3(py)2] (x = 0.75, 0.50, 0.25) können zudem Mischfarben der Lumineszenz erzeugt werden. Mit dem Komplex [B2O(C2O4)2(dmf)2] (dmf = Dimethylformamid) und dem Koordinationspolymer 1∞[Tb{o-C6H4(CO2)2}(H2O)6][PHB]2 (PHB− = Phthalatoborat) konnte zudem die Sonderstellung des [BSB]−-Anions deutlich gemacht werden, da es als einziges untersuchtes Spiroborat-Anion vollständig in Zielverbindungen eingebaut werden konnte, während vergleichbare Spiroborat-Anionen wie das [PHB]−-Anion in Gegenwart Lewis-acider Verbindungen hingegen die Abspaltung funktioneller Gruppen zeigten. Insgesamt konnten in dieser Arbeit somit zahlreiche neue, lumineszierende Koordinationspolymere mit Cyano- und Oxoboraten erfolgreich dargestellt werden. / Within the scope of this thesis 30 new complexes and coordination polymers could be synthesized, starting from borate-containing salts and ionic liquids (ILs) as well as lanthanide compounds. Therefore, manifold synthesis strategies were applied, including salt metatheses, solvothermal syntheses and ionothermal syntheses. The main focus within the synthesis of desired products was set on the properties of the compounds, particularly on their photoluminescence behavior. Both cyanoborates and oxoborates were investigated regarding their potential in constructing new coordination polymers. Acids and ionic liquids with dicyano-, tricyano- and tetracyanoborate anions were used, leading to diverse coordination compounds due to their varying number of cyano groups. By applying ionothermal methods, the compounds 1∞[Ln(NO3)2{B(CN)4}(H2O)4] (Ln = La, Eu) and [EMIm]1∞[LaNO3{B(CN)4}3(H2O)3] could be synthesized from the ionic liquid [EMIm][B(CN)4], showing a transformation of the ionic liquid into a coordination polymer incorporating both cation and anion of the IL. Remarkably, it is possible to control, which of the products is formed by changing the reaction temperature. Single crystals of the compound 3∞[La{C2F5B(CN)3}3] could also be synthesized by ionothermal methods. With the knowledge on the crystal structure, it was possible to identify the compounds 3∞[Ln{C2F5B(CN)3}3] (Ln = Eu, Ho) as isotypic structures, thereby allowing further investigations on their properties, including their luminescence features. By reacting lanthanide chlorides with the acid H[BH2(CN)2] in pyridine (py), one-dimensional coordination polymers [H(py)2]1∞[LnCl2{BH2(CN)2}2(py)2]·0.5py (Ln = Ce, Pr) could be obtained. Under similar solvothermal conditions, but in MeCN as solvent, the formation of networks of the constitution 3∞[Ln2{BH2(CN)2}9]·[Ln(CH3CN)9] (Ln = Ce, Eu, Tb) is observed instead. The three-dimensional coordination polymers 3∞[Ln{BH(CN)3}3] (Ln = Eu, Tb) were also synthesized in MeCN, however starting from the acid [H3O][BH(CN)3]. The compounds described show characteristic luminescence for spectroscopically relevant ions, based on 5d- 4f- and 4f-4f-transitions, respectively. Thereby, the observed luminescence is mainly based on a direct excitation of the respective lanthanide ions. With the bis-salicylatoborate-anion (= BSB−), it was possible to synthesize one-dimensional, strand-like coordination polymers 1∞[Ln(BSB)3(py)2] (Ln = Y, La – Nd, Sm) as well as twodimensional, sheet-like structures 2∞[Ln(BSB)3(py)] (Ln = Sm, Eu, Tb – Er), starting from Na[BSB] and LnCl3 under solvothermal conditions in pyridine. The molecular complex [ErCl2(py)4BSB] allowed further insights into the formation of the described compounds, as it proves a gradual substitution of chloride ligands by [BSB]−-anions. The compounds with the [BSB]−-anion show photoluminescence features ascribed to different processes. 1∞[Y(BSB)3(py)2] shows fluorescence originating from the [BSB]−-anion, while 1∞[Ln(BSB)3(py)2] (Ln = Ce, Nd, Sm) and 2∞[Ln(BSB)3(py)] (Ln = Sm, Tb, Dy) show luminescence based on 5d-4f- and 4f-4f-transitions. These are quite intense, as an antenna effect of coordinating [BSB]−-anions can be observed. The compounds 2∞[Ln(BSB)3(py)] (Ln = Eu, Ho) prove as exceptions, as direct excitation is mainly observed for Eu3+, while Ho3+ shows reabsorption processes. By mixing different contents of Eu3+ and Tb3+ in the one-dimensional coordination polymers 1∞[EuxTb1−x(BSB)3(py)2] (x = 0.75, 0.50, 0.25), it is possible to create mixed luminescence colors. With the complex [B2O(C2O4)2(dmf)2] (dmf = dimethylformamide) and the coordination polymer 1∞[Tb{o-C6H4(CO2)2}(H2O)6][PHB]2 (PHB− = phthalatoborate) the exceptional position of the [BSB]−-anions within the class of spiroborates could be revealed, as it proved as only spiroborate anion within this work, that could be fully incorporated in the desired products. This is benficial to a great extent, as similar spiroborate anions like the [PHB]−-anion tend to loose functional groups in the presence of Lewis-acid compounds. Altogether, it was possible to successfully synthesize numerous luminescent coordination polymers with cyano- and oxoborates in this work.

Die hier vorliegende Arbeit behandelt die Synthese und Charakterisierung neuer Übergangsmetall-Borate sowie auf Cyanoborat-Anionen basierende Übergangsmetallkomplexe und Koordinationsverbindungen mit N-Donor-Liganden und Triphenylphosphan. / This work outlines the synthesis and characterization of novel transition metal borates as well as transition metal complexes based on cyanoborate anions and coordination compounds with N-donor ligands and triphenylphosphine.

No description available.

Scorpionates are versatile and flexible ligands with a wide range of applications including catalysis, C-H bond activation, formation of new class of materials, and mimicking enzymatic reactions. This is as a result of its steric and electronic properties, and due to the relative ease with which the 3, and 5-positions of the pyrazole ring can be functionalized. In this work, we report the synthesis of a new class of scorpionate ligands known as cyanoscorpionates which can crosslink various metal centers. Thus, bis (4-cyano-3,5-diphenylpyrazolyl)borate BpPh2,4CN was synthesized and fully characterized by 1H NMR and FT-IR. Coordination of bis (4-cyano-3,5-diphenylpyrazolyl)borate BpPh2,4CN to thallium (I) metal was performed and characterized and we are looking to elucidating its molecular structure by X-ray crystallography in future.

Reproduction de : Thèse de doctorat : physique : Metz : 2004. / Titre provenant de l'écran-titre. Notes bibliographiques.

Thesis (M.S.) in Earth Sciences--University of Maine, 2009. / Includes vita. Includes bibliographical references (leaves 90-95).

Borate can be a potential candidate to protect building envelope components from biodegradation as it has low toxicity and can penetrate wood without pressure treatment, even in the refractory species commonly used in construction industries as structural components. In this research, wood moisture content, grain direction, formulation and species that affect the diffusion of borate in refractory species were investigated. Two highly concentrated formulations were applied and a novel approach (borate bandage) was used to keep the preservative on the surface and enhance the diffusion by reducing surface drying. From ANOVA test for different diffusion periods and depths of penetration, it was found that grain directions and moisture content are significant factors. A mould test was performed, the diffusion co-efficients were calculated and some recommendations were made about the quantity required to protect a specific volume of wood considering the distance moved by diffusion and volume treated in different directions.

Borate can be a potential candidate to protect building envelope components from biodegradation as it has low toxicity and can penetrate wood without pressure treatment, even in the refractory species commonly used in construction industries as structural components. In this research, wood moisture content, grain direction, formulation and species that affect the diffusion of borate in refractory species were investigated. Two highly concentrated formulations were applied and a novel approach (borate bandage) was used to keep the preservative on the surface and enhance the diffusion by reducing surface drying. From ANOVA test for different diffusion periods and depths of penetration, it was found that grain directions and moisture content are significant factors. A mould test was performed, the diffusion co-efficients were calculated and some recommendations were made about the quantity required to protect a specific volume of wood considering the distance moved by diffusion and volume treated in different directions.

Graduation date: 1992