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

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-(mu-Cl)(2)-Cu} complex A were calculated through BS-DFT. The variation of the Cu-(mu-Cl)-Cu angle (alpha), Cu center dot center dot center dot Cu distance (R-0), and Cu-Cl-Cu-Cl dihedral angle (tau) followed by structural optimization and calculation of the magnetic coupling constant (J(calc)) revealed several trends. J(calc) increased linearly with R-0 and tau, and initially increased and then decreased with alpha. 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- < N-3(-) < F-). Furthermore, a linear relationship was found between the spin density of the bridging ligand and J(calc).

Automated summary

Theoretical understanding of magneto-structural correlations in dichloro-bridged dicopper(II) complexes can guide the design of magnetic materials having broad-scale applications. Previous reports suggest these correlations are complicated and unclear. Magnetic coupling constants (J(calc)) of variants of a representative {Cu-(mu-Cl)(2)-Cu} complex A were calculated through BS-DFT to clarify possible correlations. The results revealed several trends, including the linear increase of J(calc) with R-0 and tau, and the initial increase and then decrease with alpha. Bridging ligand effects on J(calc) for dicopper(II) complexes were also evaluated through BS-DFT, showing an increase with increasing ligand field strength and a linear relationship between the spin density of the bridging ligand and J(calc).