Magneto-structural maps and bridged-ligand effect for dichloro-bridged dinuclear copper(ii) complexes: a theoretical perspective.

ABSTRACT: Theoretical understanding of magneto-structural correlations in dichloro-bridged dicopper(ii) complexes can guide the design of magnetic materials having broad-scale applications. However, previous reports suggest these correlations are complicated and unclear. To clarify possible correlations, magnetic coupling constants (J _calc) of variants of a representative {Cu-(μ-Cl)₂-Cu} complex A were calculated through BS-DFT. The variation of the Cu-(μ-Cl)-Cu angle (α), Cu⋯Cu distance (R ₀), and Cu-Cl-Cu-Cl dihedral angle (τ) followed by structural optimization and calculation of the magnetic coupling constant (J _calc) revealed several trends. J _calc increased linearly with R ₀ and τ, and initially increased and then decreased with α. Further, bridging ligand effects on J _calc for dicopper(ii) complexes were evaluated through BS-DFT; the results revealed that J _calc increased with increasing ligand field strength (I^- < Br^- < Cl^- < N₃ ^- < F^-). Furthermore, a linear relationship was found between the spin density of the bridging ligand and J _calc.

SUBMITTER: Luo S 

PROVIDER: S-EPMC10116190 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature