From computational studies on the mechanism of the formation of organic meterocyclic compounds to spin crossover studies in Prussian Blue

摘要

Understanding with the use of computational tools the mechanism of reactions in organic chemistry or the electronic transitions in solid state is a quite challeng- ing problem. The main methods utilised for this research are Density Functional Theory (DFT) and time dependent DFT. The software utilised is GAUSSIAN03 for the reaction mechanism studies and CRYSTAL06 for the study of the spin crossover transition in a Prussian Blue analogue. In chapter 2, we investigate the first two reaction steps of the synthesis reaction mechanism of Dihydro-Imidazo-Phenathridinium (DIP) derivatives, which are a novel class of compounds that intercalate DNA, possessing anticancer properties. In chapter 3, we examine the last step of the DIP synthesis reaction, which is a hydride transfer, in particular it is considered the solvent effect on the excitation energies of the molecules involved in the hydride transfer. In chapter 4, we consider the hydride transfer reaction of heteroaryl-dimethylbenz- imidazoline derivatives (HDBMZ-H) with benzyl-carbamoylpyridinium (BCPY) and benzyl-nitrosoquinolinium (BNIQ) ions. In chapter 5, we study the spin crossover transition (SCO) in the CsFeII[CrIII(CN)6] Prussian Blue analogue. This transition can be induced experimentally by varia- tions of temperature or pressure and more light on this mechanism can be useful in information processing and display technologies. Those fields, in fact can benefit from the application of molecular electronic bistabilities in which the SCO phe- nomenon can be classified.