Lanthanide bisphthalocyanine single-molecule magnets: A DFT survey of their geometries and electronic properties from lanthanum to lutetium

By using density functional theory (PBE and Grimme's dispersion correction) we studied how a stepwise addition of 4f electrons influences the geometries electronic properties lanthanide bisphthalocyanine (LnPc2) single-molecule magnets (SMMs). To handle convergence problems, which are common for compounds, tested DN, DND DNP basis sets. The calculations all fifteen bisphthalocyanines were possible to complete only with DN set, optimized in reasonable agreement experimental X-ray diffraction data; on other hand, use produces problems unrealistic geometries. Selected parameters including HOMO, LUMO, HOMO-LUMO gap energies, charge spin central metal atom calculated set analyzed. In case closed-shell ions La3+ Lu3+ no transfer phthalocyanine ligands is observed. most complexes (Ce, Pr, Tb–Yb) unpaired transferred ligands, whereas Nd–Eu, Ln increases. unexpected observation loss sole f-electron cerium, means that its oxidation state Ce4+ not Ce3+: this converts CePc2 into species.