From computational studies on the mechanismof the formation of organic meterocycliccompounds to spin crossover studies inPrussian Blue

QD Chemistry

Portinari, Damiano ; Wilson, Chick

University:University of Glasgow

Department:School of Chemistry

关键词: Computational Chemistry, reaction mechanism, solvent effect, spin crossover transition, Prussian Blue;   

Others  :  http://theses.gla.ac.uk/1779/1/2009portinariphd.pdf

来源: University of Glasgow

【 摘 要 】

Understanding with the use of computational tools the mechanism of reactions inorganic chemistry or the electronic transitions in solid state is a quite challeng-ing problem. The main methods utilised for this research are Density FunctionalTheory (DFT) and time dependent DFT. The software utilised is GAUSSIAN03for the reaction mechanism studies and CRYSTAL06 for the study of the spincrossover transition in a Prussian Blue analogue.In chapter 2, we investigate the first two reaction steps of the synthesis reactionmechanism of Dihydro-Imidazo-Phenathridinium (DIP) derivatives, which are anovel class of compounds that intercalate DNA, possessing anticancer properties.In chapter 3, we examine the last step of the DIP synthesis reaction, which is ahydride transfer, in particular it is considered the solvent effect on the excitationenergies 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 ininformation processing and display technologies. Those fields, in fact can benefitfrom the application of molecular electronic bistabilities in which the SCO phe-nomenon can be classified.