title: Structures and spectroscopic properties of bis(phthalocyaninato) yttrium and lanthanum complexes: theoretical study based on density functional theory calculations.
abstract: 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.
authors.affiliation: Department of Chemistry, Shandong University, Jinan 250100, China.
authors.forename: Yuexing
authors.initials: Y
authors.lastname: Zhang
authors.forename: Xue
authors.initials: X
authors.lastname: Cai
authors.forename: Yang
authors.initials: Y
authors.lastname: Zhou
authors.forename: Xianxi
authors.initials: X
authors.lastname: Zhang
authors.forename: Hui
authors.initials: H
authors.lastname: Xu
authors.forename: Zhongqiang
authors.initials: Z
authors.lastname: Liu
authors.forename: Xiyou
authors.initials: X
authors.lastname: Li
authors.forename: Jianzhuang
authors.initials: J
authors.lastname: Jiang