Structures and spectroscopic properties of bis(phthalocyaninato) yttrium and lanthanum complexes: Theoretical study based on density functional theory calculations

Density functional theory (DFT) calculations were carried out to describe the molecular structures, molecular orbitals, atomic charges, UV-vis absorption spectra, IR, and Raman spectra of bis(phthalocyaninato) rare earth(III) complexes M(Pc)(2) (M = Y, La) as well as their reduced products [M(Pc)(2)](-) (M = Y, La). Good consistency was found between the calculated results and experimental data. Reduction of the neutral M(Pc)(2) to [M(Pc)(2)](-) induces the reorganization of their orbitals and charge distribution and decreases the inter-ring interaction. With the increase of ionic size from Y to La, the inter-ring distance of both the neutral and reduced double-decker complexes M(Pc)(2) and [M(Pc)(2)](-) (M = Y, La) increases, the inter-ring interaction and splitting of the Q bands decrease, and corresponding bands in the IR and Raman spectra show a red shift. The orbital energy level and orbital nature of the frontier orbitals are also described and explained in terms of atomic character. The present work, representing the first systemic DFT study on the bis(phthalocyaninato) yttrium and lanthanum complexes sheds further light on clearly understanding structure and spectroscopic properties of bis(phthalocyaninato) rare earth complexes.