Electronic Structures, and Optical and Magnetic Properties of Quadruple-Decker Phthalocyanines

Abstract

For applications of magnetic devices with operating nuclear-spin-based quantum bits in quantum computing, electronic structures, and magnetic and optical properties of quadruple-decker phthalocyanines with 3d transition metals, such as scandium, yttrium, and lanthanum atoms (M3Pc4: M = Sc, Y, and La), were studied by quantum calculation using density function theory. Electron density distributions at the highest occupied molecular orbital and lowest unoccupied molecular orbital were considerably delocalized on the phthalocyanine ring with considerable bias of the electrostatic potential. The wide energy gaps and the ultraviolet-visible-near infrared spectra of the systems were based on the phthalocyanine ring-ring interactions with overlapping π-orbitals on the phthalocyanine rings. The chemical shift behavior of 13C and 14N-NMR of Sc3(Pc)4, Y3(Pc)4, and La3(Pc)4 depended on the deformation of their structures owing to Jahn-Teller splitting of the d-orbital in the metal ligand field, the considerable perturbation of the metal ligand crystal field on the phthalocyanine ring, the electronic structure based on the electron density distribution, and the magnetic interaction of the nuclear quadrupole interaction. The magnetic parameters of the principle g-tensor, the V-tensor of the electronic field gradient, and the asymmetric parameters were influenced by the deformed structures of the complex with the considerable deviation of the charge density distribution. The quadruple-decker metal phthalocyanines using 3d transition metals have an advantage in controlling the electronic structure and magnetic parameters based on the nuclear spin interaction in spin lattice relaxation with respect to applications of single-molecular magnets.