DFT study of conjugated molecular systems containing transition metals

Abstract

This thesis explores the structural, electronic, and photophysical properties of two distinct classes of transition metal complexes platinum-based molecular wires and fluorinated metallocorroles (Re, Os, Au) using advanced computational methodologies. The study integrates density functional theory (DFT), time-dependent DFT (TD-DFT), and nonequilibrium

Green’s function (NEGF) techniques to elucidate key structure-property relationships and their implications for functional applications. For platinum molecular wires, DFT-NEGF calculations reveal that conjugated carbon chains mediate coherent electron transport, with conductance exhibiting exponential length dependence. Oxidation studies show spin density localization on the organic backbone rather than platinum centers, highlighting the role of ligand design in modulating redox properties. In fluorinated metallocorroles, fluorination enhances metal-ligand stability, electronic gaps, and photophysical performance, as evidenced by TD-DFT/PCM simulations of UV-Vis spectra and frontier orbital analyses. These findings align with experimental data, demonstrating the predictive power of computational tools. The results underscore the potential of tailored molecular engineering for applications in molecular electronics, photodynamic therapy, and catalysis. By bridging theoretical insights with experimental validation, this work advances the rational design of high-performance organometallic systems and paves the way for future studies on dynamic processes and broader metal-ligand architectures