Inverse and regular phenyl-azole ligands for luminescent Iridium(III) complexes

In the modern society, light is mostly powered by electricity which lead to a significant increase of the global energy consumption. In order to reduce it, different kinds of electric lamps have been developed over the years; it is now accepted that phosphorescence-based OLEDs offer many advantages over existing light technologies. Iridium complexes are considered excellent candidates for bright materials by virtue of the possibility to easily tune the wavelength of the emitted radiation, by appropriate modifications of the nature of the ligands. It is important to note that the synthesis of Ir(III) blue-emitting complexes is a very challenging goal, because of wide HOMO-LUMO gaps needed for produce a deep blue emission. During my thesis I planned the synthesis of two different series of new Ir(III) heteroleptic complexes, the C and the N series, using cyclometalating ligands containing an increasing number of nitrogens in inverse and regular position. I successfully performed in the synthesis of the required four ligands, i.e. 1-methyl-4-phenyl-1H-imidazole (2), 4-phenyl-1-methyl-1,2,3-triazole (3), 1-phenyl-1H-1,2,3-triazole (6) and 1-phenyl-1H-tetrazole (7), that differ in the number of nitrogens present in the heterocyclic ring and in the position of the phenyl ring. Therefore the cyclometalation of the obtained ligands to get the corresponding Ir(III)-complexes was attempted. I succeeded in the synthesis of two Ir(III)-complexes of the C series, and I carried out various attempts to set up the appropriate reaction conditions to get the remaining desired derivatives. The work is still in progress, and once all the desired complexes will be synthesized and characterized, a correlation between their structure and their emitting properties could be formulated analysing and comparing the photophysical data of the real compounds.

Studio del trapping adiabatico per mappe stocastiche

In questa tesi vengono trattati argomenti relativi alla dinamica dei fasci di particelle: in particolare si è preso in considerazione il moto betatronico di una particella carica all'interno di un acceleratore circolare. Vengono quindi discussi alcuni aspetti della dinamica trasversa introducendo il formalismo Hamiltoniano e discutendo il modello presentato da Hénon per il caso bidimensionale. Viene poi introdotta la teoria adiabatica al fine di studiare gli effetti intrappolamento di un ensemble di particelle. Infine vengono presentate alcune simulazioni che permettono di poter osservare come il rumore rappresenti un fattore di rilevante importanza nello studio di tali fenomeni.

Direct C–H silylation and borylation of biomass derivatives by iridium heterogeneous catalysts

Furfural and its derivatives represent renewable and readily available platforms for a wide range of chemicals. Much attention has been devoted to their functionalization over the last years. TM-catalysed C–H activation has emerged as a powerful tool for synthesizing new C–C and C–X bonds. Moreover, it provides a sustainable way to obtain molecules by reducing waste and saving steps. At the same time, iridium catalysts have proven to be very active in some C–H functionalizations of several (hetero)arenes. Although very promising, this technique is still poorly applied on an industrial scale due to the severe conditions required. Continuous flow chemistry using heterogeneous catalysts appears to be a valuable way to overcome these problems. In this work, we present different solutions for the immobilization of homogeneous iridium complexes on silica gels, using bidentate amines and phosphines as anchoring ligands. We successfully employed the catalysts in C–H silylation and borylation of furfural, using C2 located directing group. In this way, we finally obtained a suitable catalyst that could be potentially applied in continuous-flow chemistry.

Complessi carbenici N-eterociclici di rutenio: catalizzatori omogenei in reazioni di idrogenazione e deidrogenazione

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 bifunzionali metallo-legante da impiegare in reazioni di catalisi omogenea, in particolare in reazioni redox quali idrogenazione e deidrogenazione attraverso il trasferimento di idrogeno. Il mio progetto ha riguardato la messa a punto della sintesi di complessi di Ru(0) che combinano leganti ciclopentadienonici e carbeni N-eterociclici e la sintesi dei corrispondenti complessi cationici per protonazione. Inoltre, è stato sintetizzato e caratterizzato un nuovo complesso cationico attraverso la metilazione del corrispettivo complesso neutro. I complessi sintetizzati sono stati utilizzati come precursori di catalizzatori nella riduzione tramite trasferimento di idrogeno del 4-fluoroacetofenone, valutandone l’attività catalitica in relazione a leganti, additivi e controioni. Allo scopo di delineare qualche ipotesi sul meccanismo di reazione sono stati effettuati diversi studi sulla reattività dei complessi impiegati in catalisi, in particolare usando la piridina come agente di “trapping”. Infine, è stato condotto uno studio preliminare dell’attività catalitica dei complessi sintetizzati nell’ossidazione di benzilalcol a benzaldeide. The present work is part of a research project that involves the study of new ruthenium-based transition metal complexes in order to develop new metal-ligand bifunctional catalysts to employ in homogeneous catalytic systems, in particular in redox reactions such as hydrogenation and dehydrogenation through hydrogen transfer. My project is focused on the optimization of the synthesis of Ru(0) complexes that combines different ligands as tetraphenylcyclopentadienone and N-heterocyclic carbenes and the synthesis of the corresponding cationic complexes by protonation. Furthermore, it is reported the synthesis and characterization of a new cationic complex obtained by methylation of the corresponding neutral complex. All the prepared complexes were employed as catalyst precursors in the transfer hydrogenation of 4-fluoroacetophenone and their performances were investigated in relation to the type of ligands, additives and counterions. The reactivity of these ruthenium complexes was also investigated with the aim of delineate some hypothesis on the reaction mechanism, in particular employing pyridine as a trapping agent. Finally, preliminary studies on the oxidation of benzyl alcohol have been carried out.

Development of tandem C-H borylation/functionalization procedures for late stage functionalization of compounds

The development of procedures for the iridium catalyzed C-H borylation of 1-aryl pyrazolopyrimidines and 1-aryl indazoles is reported. Investigation on the activity of the catalyst revealed the combination of an iridium (I) precursor and tetramethylphenantroline as the best catalytic system. Moreover, the procedures are regioselective resulting in the selective borylation of different C-H bonds within the substrates. The application of C-H borylation to late stage functionalization is demonstrated: a biologically active compound in AstraZeneca's project underwent tandem borylation/oxidation reaction, in order to obtain a functionalized product containing an OH group.

Efficiency limits for silicon/perovskite tandem solar cells: a theoretical model

The primary goal of this work is related to the extension of an analytic electro-optical model. It will be used to describe single-junction crystalline silicon solar cells and a silicon/perovskite tandem solar cell in the presence of light-trapping in order to calculate efficiency limits for such a device. In particular, our tandem system is composed by crystalline silicon and a perovskite structure material: metilammoniumleadtriiodide (MALI). Perovskite are among the most convenient materials for photovoltaics thanks to their reduced cost and increasing efficiencies. Solar cell efficiencies of devices using these materials increased from 3.8% in 2009 to a certified 20.1% in 2014 making this the fastest-advancing solar technology to date. Moreover, texturization increases the amount of light which can be absorbed through an active layer. Using Green’s formalism it is possible to calculate the photogeneration rate of a single-layer structure with Lambertian light trapping analytically. In this work we go further: we study the optical coupling between the two cells in our tandem system in order to calculate the photogeneration rate of the whole structure. We also model the electronic part of such a device by considering the perovskite top cell as an ideal diode and solving the drift-diffusion equation with appropriate boundary conditions for the silicon bottom cell. We have a four terminal structure, so our tandem system is totally unconstrained. Then we calculate the efficiency limits of our tandem including several recombination mechanisms such as Auger, SRH and surface recombination. We focus also on the dependence of the results on the band gap of the perovskite and we calculare an optimal band gap to optimize the tandem efficiency. The whole work has been continuously supported by a numerical validation of out analytic model against Silvaco ATLAS which solves drift-diffusion equations using a finite elements method. Our goal is to develop a simpler and cheaper, but accurate model to study such devices.