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. 2023 Apr 20;13(18):12430-12437.
doi: 10.1039/d3ra00585b. eCollection 2023 Apr 17.

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

Shuchang Luo  1   2   3 , Xianwei Shen  1   2 , Peng Gao  1   2 , Ting Tu  1   2 , Xiaoyuan Sun  1   2
Affiliations

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

Shuchang Luo et al. RSC Adv. .

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.

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Conflict of interest statement

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Figures

Fig. 1
Fig. 1. Molecular structure of complex A.
Fig. 2
Fig. 2. Local molecular magnetic orbitals in BS state of complex A (isovalue: 0.05; yellow (+); cyan (−); (a) the paramagnetic center is Cu(1); (b) the paramagnetic center is Cu(2)).
Fig. 3
Fig. 3. Singly occupied magnetic orbitals in HS state of complex A (isovalue: 0.05; yellow (+); cyan (−); (a) it represents one SOMOs of the complex A in the high spin state; (b) it represents another SOMOs of the complex A in the high spin state).
Fig. 4
Fig. 4. Spin density diagram of HS state and BS state for complex A (isovalue: 0.003; yellow (+); cyan (−); (a) spin density for complex A in the HS state; (b) spin density for complex A in the BS state).
Fig. 5
Fig. 5. Magneto–structural correlation of Jcalc and R0 by BS-DFT. (a) Jcalc–R0 magneto–structural correlation; (b) spin density variation of Cu(ii) and bridging ligand Cl− in the triplet state (S = 1).
Fig. 6
Fig. 6. Magneto–structural correlation of Jcalcversus bond angle (α) obtained by BS-DFT calculations. (a) Jcalc-α magneto–structural correlation; (b) spin density variation of Cu(ii) and bridging ligand Cl− in the triplet state (S = 1).
Fig. 7
Fig. 7. Magneto–structural correlation of Jcalcversus Cu–Cl–Cu–Cl dihedral angle (τ) obtained by BS-DFT calculations. (a) Jcalc-τ magneto–structural correlation; (b) spin density variation of Cu(ii) and bridging ligand Cl− in the triplet state (S = 1).
Fig. 8
Fig. 8. Magneto–structural correlation of Jcalcversus the parameter α/RCu–Cl from BS-DFT calculations. (a) Jcalcversus α/RCu–Cl parameter for fixed R0; (b) Jcalcversus α/RCu–Cl parameter for fixed α; (c) Jcalcversus α/RCu–Cl parameter for fixed τ.
Fig. 9
Fig. 9. Magneto–structural correlation of Jcalc and ligands were obtained by BS-DFT (Model I). (a) The magneto–structural correlation of Jcalc-ligand; (b) spin density variation of Cu(ii) and bridging coordination atoms in the triplet state (S = 1).
Fig. 10
Fig. 10. Magneto–structural correlation of Jcalcversus the spin density of the bridging ligand coordinating atoms by BS-DFT.
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