Theoretical studies on dicopper(II) complexes of phenoxido-bridged ligands: Magneto-structural correlations

• DOI: 10.1016/j.comptc.2021.113524
• Publication Date: 2021-11-22T17:15:22Z
• Authors: Shuchang Luo; Yangyang Su; Yingli Wang; Xiaoyuan Sun
• Keywords: 02 engineering and technology; 0210 nano-technology

Abstract In this work, the magnetic properties of the phenoxido-bridged binuclear copper complex [Cu2(LMe,Me,Me)2] were studied using the density functional theory-broken symmetry method by employing various functionals and basis sets, and the magneto-structural correlation was established. Encouraging results were obtained using the wB97X/def2-TZVPP level of theory, as the calculated magnetic coupling constant (−198.03 cm−1) was close to the experimental value (−197.55 cm−1). Molecular magnetic orbital and spin density analyses proved that the molecular magnetic orbital is composed of Cu(1)/Cu(2) 3 d z 2 orbitals and phenoxido-bridged ligand-conjugated π-type molecular orbitals, and the paramagnetic centers are dominated by spin delocalization. The magneto-structural correlation proved that the magnetic coupling constant of the complex initially increases and subsequently decreases with increase inthe Cu O Cu bond angle (θ). As the bond angle (θ) increases, the character of the exchange is altered from ferromagnetic to antiferromagnetic.