Bis[octakis(2,6-dimethylphenoxy)phthalocyaninato] rare earth(III) complexes: Structure, spectroscopic, and electrochemical properties

Abstract Homoleptic bis(phthalocyaninato) rare earth complexes MIII[Pc(β-DMPO)8]2 [Pc(β-DMPO)8 = 2, 3, 9, 10, 16, 17, 23, 24-octakis(2,6-dimethylphenoxy) phthalocyaninate; M = Pr, Nd and Sm] have been synthesized and characterized by a series of spectroscopic methods including matrix-assisted laser desorption/ionization time of flight mass spectrometry, nuclear magnetic resonance spectrum, electronic absorption and infrared spectroscopy. Their molecular structures have been determined by single crystal X-ray diffraction analysis and electrochemical properties studied by cyclic voltammetry. The electrochemical studies illuminate the electron-withdrawing nature of these substituents in the double-deckers. Density functional theory (DFT) calculations are carried out to further clarify the electron transition nature and orbital information. Based on the structural, spectroscopic, electrochemical and theoretical studies, we found that the substitution effect as well as the size of the metal centers altered the molecular and electronic structures significantly.