Theoretical investigation of the effect of auxiliary ligands on dipyrazole-bridged binuclear Cu(II) complexes

• Published in: Chemical physics letters 2021-12, Vol.784, p.139102, Article 139102
• Main Authors: Luo, Shuchang, Xu, Ce, Zhang, Rou, Sun, Xiaoyuan
• Format: Article
• Language: English
• Subjects: 3,5-bis(2-pyridyl)pyrazolate; Auxiliary ligand; Binuclear Cu(II) complex; DFT-BS
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2021.139102

[Display omitted] •DFT-BS simulations at the B1LYP/def2-TZVPP level of theory are employed for the investigation of magnetic coupling constant of 3,5-bis (2-pyridyl) dipyrazolate bridged binuclear Cu(II) complex (anti-[Cu2(bpypz)2(DCNE)2]).•Molecular magnetic orbital and spin population analyses showed that the spin delocalization mechanism is operational at the paramagnetic Cu(II) centers.•Intr oduction of auxiliary ligands in this complex increased the value of S2 between the non-orthogonal magnetic orbitals of the complex and the paramagnetic Cu(II) centers. The anti-configuration of a 3,5-bis(2-pyridyl)dipyrazolate-bridged binuclear Cu(II) complex (anti-Cu2(bpypz)2(DCNE)2) and its magnetostructural correlations were studied at the B1LYP/def2-TZVPP level of theory. The calculated magnetic coupling constant was consistent with the experimental value. Molecular magnetic orbital and spin population analyses demonstrated that the spin delocalization mechanism is operational at the paramagnetic Cu(II) centers. The introduction of auxiliary ligands to this complex increased the value of the square of the overlap integral between the non-orthogonal magnetic orbitals of the complex and the paramagnetic Cu(II) centers. The magnetic coupling constant decreased with increasing antiferromagnetic contribution.