Abstract: Dimeric dimethylAluminum complexes, [Me2Al(m-R)]2 (R= Me, NiPr2, NiBu2, NPh2, NHnBu, OMe) and Al(NiPr2)3 react with carbon dioxide, yielding a series of carbamato aluminum complexes: [Me2Al(m-OCMe3)]2 (1); [Me2Al(m-O2CNiPr2)]2 (2); [Me2Al(m-O2CNiBu2)]2 (3); [Me2Al(m-O2CNPh2)]2 (4); [Me2Al(m-O2CNHnBu)]2 (5); Al4Li2(m4-O)2(m-O2CNiPr2)10 (6). X-ray crystallographic determinations were performed on compounds (2), (3), (4) and (6). The general trends identitide in these structures suggest that depending upon the bonding energy of aluminum with bridge ligand and electron density on bridge ligand. One novel crystal structure (6), Al4Li2(m4-O)2(m-O2CNiPr2)10 , was found from the previous reaction in the presence of lithium chloride. These compounds were characterized with 1H, 13C NMR, IR spectroscopy, mass spectrometer, and elemental analyses.

Bulky 1,4-diamines 1,2-[2,4,6-(CH3)3-C6H3NH-CH2]2-C6H4 and 1,2-(2,6-iPr2C6H3NHCH2)2-C6H4 were utilized as pro-ligands for the formation of novel three-coordinate aluminum alkyl compounds with the general formula [(1,4-diamido)AlR], where R = Me or Et. The synthesis of analogous aluminum hydrides was also explored resulting in the formation of four-coordinate complexes incorporating bridging hydrides. The three-coordinate aluminum complexes were developed as single-component catalysts in the ring opening polymerization of cyclic esters. The main focus was on caprolactone polymerization, but other monomers were explored, including lactide, butyrolactone, cis-cyclooctene, and diphenylacetylene. The mechanism of polymerization with caprolactone was also studied. The coordination chemistry of other metals and non-metals with the 1,4-diamido ligands were also investigated. Phosphorus, boron, zinc, and zirconium were the main focus. [(1,4-diamido)PCl] complexes were successfully synthesised as precursors to the formation of cationic phosphenium species, [(1,4-diamido)P]+.

Abstract This thesis focuses on the molecular-level chemistry of the solvation of aluminum salts. Fundamental aspects such as, structural characteristics of the aluminum molecules, hydrolysis, acidity, solvation structure, effect of counter ions, and chemical stability are discussed herein. Static computations augmented with the conductor-like screening model (COSMO) were used to investigate hundreds of planar and cyclic configurations of dimeric, trimeric, tetrameric, and pentameric aluminum complexes. Car–Parrinello molecular dynamics (CPMD) calculations were used to expand investigations to aqueous environments. This thesis consists of four articles and one additional article. The first paper focuses on the structural analysis of the hydrolysis products of AlCl3 · 6H2O. Dimeric, trimeric, and tetrameric aluminum (chloro)hydroxides were investigated in both gas and liquid phase. The liquid environment was modeled by using COSMO. The second and the additional paper concentrate on the chemistry of aluminum sulfate complexes. The second article focuses on identifying hydrolysis products of AlCl3 · 6H2O in the presence of sulfate (H2SO4). The additional paper focuses on the structural characteristics of the hydrolysis products of Al2 (SO4)3 · 18H2O. Structural information was deduced from the ESI MS results with the aid of computational methods. Detected cationic structures closely resembled the aluminum chlorohydrate analogues introduced in the first paper. The third and fourth articles are devoted to the hydrolysis, stability, and dynamics of dimeric and pentameric aluminum (chloro)hydroxides in aquatic environments. During the CPMD simulations, several spontaneous associative hydration reactions were detected in the primary hydration shell of the complexes. Dimeric aluminum chlorohydrates were detected to be stable in liquid conditions, whereas the pentameric aluminum complexes experienced significant topological changes during the simulations. Constrained simulations were used to reveal the role of chloride ions in the hydrolysis processes of dimeric complexes. The effect of the empirical van der Waals corrections to the dynamics of the simulations was also tested for the pentameric system. The results of this thesis showed unequivocally that computational chemistry provides effective tools for structural analysis of inorganic complexes such as, aluminum chlorohydrates and sulfates in both gas and liquid phase. In addition, calculations provided answers to the anomalies detected in the experiments. Hence, theoretical methods are highly recommended to be used alongside with conventional experimental methods in the interpretation of the aluminum species in aqueous solutions and to widen the overall chemical perspective of the hydrolysis of aluminum salts.

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Les semi-conducteurs organiques à base d’aluminium ont été systématiquement synthétisés et caractérisés par méthodes photo-physiques et électrochimiques. Une étude de leur relation structure-propriétés électroniques a été menée. Les orbitales frontières ont été comparées à celles obtenues par calcul. De nouvelles méthodes ont été utilisées permettant une description de la morphologie des SCOs et un calcul de mobilité des porteurs de charges associés. La mobilité des trous dans Al(Op)3 a été mesurée sur des transistors en film minces: 0.6-2.1×10−6cm2V−1s−1. Par des techniques de spectroscopie en photoémission, la surface de l’hybride Co/Al(Op)3 a été sondée, révélant deux états d’interfaces hybrides, où la polarisation de spin de HIS1 est 8% plus élevée comparée au cobalt nu, et 4% plus faible dans HIS2. Enfin, des aimant moléculaires à base de phénalényle ont été étudiés. [Dy(Op)2Cl(HOp)(EtOH)] présente notamment un gap énergétique de 43.8K et un temps de relaxation de 5x10-4 s. / Aluminum-based organic semiconductors (OSCs) were systematically synthesized and studied by photophysical and electrochemical methods to identify a relationship between their chemical structure and electronic properties, using Alq3 as benchmark. Experimental HOMO and LUMO were compared to those computed. In addition, newly developed methods were implemented to generate morphologies and calculate charge carrier mobilities. The hole mobility of Al(Op)3 was measured in thin film transistors: 0.6-2.1×10−6 cm2V−1s−1. By photoemission spectroscopy techniques, the Co/Al(Op)3 hybrid interface was probed. Two hybrid interface states (HISs) were unraveled; the SP (spin polarization) of HIS1 is 8% higher than bare cobalt, whereas the SP of HIS2 is 4% lowered. At last, phenalenyl-based dysprosium SMMs (single-molecule magnet) were investigated. [Dy(Op)2Cl(HOp)(EtOH)] showed an energy gap of 43.8K and a quantum relaxation time of 5x10-4s.