Synthesis of Metal-Binding Ligand-Containing Copolymers, Nanoparticles and Blends

In this thesis we developed three copper-containing systems. Copper shows intriguing abilities in photocatalysis, however, one of the major limitations of many copper complexes is that photochemical properties might be quenched in solution caused by π-interactions between solvent and solute, due to Jahn-Teller distortion in the excited state. As such, we herein seek to synthesise copper heteroleptic complexes that will subsequently be nanoprecipitated with a polymer. This will allow the polymer to encase the complex and prevent the solvent-induced quenching. Subsequently, the preparation of blends of polymer with the aforementioned copper complexes, at different weight ratios is sought. The preparation of the blend is particularly interesting as the catalytic properties are anticipated to be inferior on account of the low surface area. However, owing to the polymer matrix better, mechanical properties are anticipated. The blends can combine the mechanical properties of the polymer and the luminescence of the complex, with the advantage that the polymer matrix can also prevent quenching from oxygen. As final task, we developed a copper-containing monomer. The synthesis of a monomer that contains copper and can be excited under ultraviolet (UV) light is particularly interesting.

Synthesis of manganese organometallic complexes

Il presente lavoro di tesi si inserisce in un progetto di ricerca volto alla sintesi di nuovi complessi di metalli di transizione per lo sviluppo di catalizzatori da impiegare in reazioni di catalisi omogenea. In particolare il mio progetto si è concentrato sulla sintesi di complessi organometallici di manganese con leganti carbenici N-eterociclici (NHC). La scelta dei leganti è stata effettuata in modo tale da poter avere leganti chelanti NHC di tipo MIC (mesoionic carbene) sintetizzati tramite cicloaddizione tra un alchino ed un azide catalizzata da rame (CuAAC) e N-alchilazione. Lo studio di questi complessi a base di manganese è ancora tutt’oggi agli albori, leganti NHC vengono molto utilizzati grazie alla possibilità di variarne le proprietà steriche ed elettroniche e alla possibilità di formare legami forti con quasi tutti i metalli. Il manganese è stato scelto poiché un elemento abbondante, poco tossico e poco costoso. The present thesis work is part of a research project aimed at the synthesis of new transition metal complexes to be used in homogeneous catalysis reactions. In particular my project focused on the synthesis of manganese organometallic complexes with N-heterocyclic carbene ligands (NHC). The choice of ligands was carried out to have NHC chelating ligands of the class of MIC (mesoionic carbene). These ligands are synthesized by cycloaddition between alkyl and azide with a copper-catalyzed reaction (CuAAC) and N-alkylation in order to obtain MIC after deprotonation. The study of these manganese-based complexes is still in its infancy today, NHC ligands are widely used thanks to the possibility of varying their steric and electronic properties and the possibility of forming strong bonds with almost all metals. The choice of manganese was made because is an abundant, low-toxic and inexpensive element.

Cube Complexes and Virtual Fibering of 3-Manifolds.

Una 3-varietà si dice virtualmente fibrata se ammette un rivestimento finito che è un fibrato con base una circonferenza e fibra una superficie. In seguito al lavoro di geometrizzazione di Thurston e Perelman, la generica 3-varietà risulta essere iperbolica; un recente risultato di Agol afferma che una tale varietà è sempre virtualmente fibrata. L’ingrediente principale della prova consiste nell’introduzione, dovuta a Wise, dei complessi cubici nello studio delle 3-varietà iperboliche. Questa tesi si concentra sulle proprietà algebriche e geometriche di queste strutture combinatorie e sul ruolo che esse hanno giocato nella dimostrazione del Teorema di Fibrazione Virtuale.

Synthesis and metal complexes of C2 symmetric ligands obtained from (R)-(+)-Betti and dialdehydes for asymmetric induction reactions

The aim of this master’s research thesis was the employment of an enantiopure 1,3-aminoalcohol, the 1-(α-aminobenzyl)-2-naphthol, known as Betti base, for the synthesis of some novel compounds which show a C2 symmetry. Some of these compounds, after derivatization, were used as ligands in association with transition metals to prepare some catalysts for enantioselective catalytic reactions. Some aminoalcohol (Salan-type) derivatives of these compounds were obtained upon reduction and in some cases it was possible to obtain complexes with transition metals such as Mn, Ni, Co and Cu. Furthermore a novel 6-membered analogue bisoxazoline ligand, 2,6-bis((R)-1-Phenyl-1H-naphtho[1,2-e][1,3]oxazin-3-yl)pyridine, was obtained and from it two Cu-complexes were prepared. The metal complexes were employed in some reactions to test the asymmetric induction, which was in some cases up to discrete values.

Synthesis and characterization of heteroleptic Cu(I) complexes based on quinolin-yl-1,2,3-triazole and pyridin-yl-1,2,3 triazole

The present work is part of a research project that involves the study of new copper based complexes to be employed as photosensitizer in carbon dioxide photoreduction reaction. My research project is focused on the synthesis and characterization of 1,2,3 triazoles with a quinoline or pyridine in the lateral chain, which have been successively utilized to synthesize heteroleptic Cu(I) complexes. Redox potential and photophysic properties have been studied.

Design, preparazione e studio applicativo di nuovi metallopolimeri luminescenti a base di complessi ciclometallati di Ir(III)

The research project of my experimental thesis deals with the design, synthesis and characterization of a new series of luminescent metallapolymers to be exploited for their peculiar photophysical and opto-electronic properties. To this end, our design strategy consisted in the incorporation of brightly luminescent and colour tuneable Ir(III) cyclometalated complexes with general formula [Ir(C^N)2(N^N)]+, where C^N represents various phenyl piridine based cyclometalating ligands and N^N is an aromatic chelating N-heterocyle, into methyl methacrylate (MMA) based copolymers. Whereas the choice of the cyclometalating ligands was driven by the possibility to obtain different emission colours, the design of the N^N ligands was aimed to obtain a molecule capable of providing the chelate coordination to the metal centre and, at the same time, of being susceptible to polymerisation reactions. To fulfil these requirements, a new molecule (abbreviated as L) consisting in an alkylated 2-pyrydyl tetrazole structure equipped with a styryl unit was designed and successfully prepared. The preparation of the target cationic metallapolymers was accomplished by the complexation of the preformed MMA-L copolymers with different amounts of an appropriate Ir(III) dimeric precursor [(Ir(C^N)2Cl)2]. The investigation of the photophysical features of the new hybrid compounds in the solid state at r.t. suggested how these metallapolymers displayed brightly intense phosphorescent emissions, whose colour was found to span from blue to yellow according to the nature of the cyclometalating ligands. In all cases, the emissive performances were superior to those displayed by the corresponding mononuclear “model” complexes. These promising results pave the way for the application of this new class of metallapolymers as Luminescent Solar Concentrators for the photovoltaic technology and/or to solid state lighting.