Theoretical Investigations of the Spin Hamiltonian Parameters for the Mononuclear Square Pyramidal [CuO5] Groups in Two Paddle Wheel Copper Complexes

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The spin Hamiltonian parameters (SHPs) (g factors and hyperfine structure constants) for the mononuclear square pyramidal [CuO5] groups in two paddle wheel copper complexes {Cu2(μ2–O2CCH3)4}(OCNH2CH3) and \({}_{\infty }^{3} [{\text{Cu}}_{ 2}^{\text{I}} {\text{Cu}}_{ 2}^{\text{II}} ( {\text{H}}_{ 2} {\text{O)}}_{ 2} {\text{L}}_{ 2} {\text{Cl}}_{ 2} ]\) are theoretically investigated from the perturbation calculations of these parameters for a rhombically elongated octahedral 3d 9 group. The slightly larger anisotropy Δg (≈ g // − g⊥) of complex 1 than complex 2 is attributed to the slightly bigger deviations of the polar angles related to the ideal value 90° and relative differences between the axial and basal Cu–O distances in the former. The axiality of the EPR signals for both systems can be illustrated as the fact that the perpendicular anisotropic contributions to X and Y components of the SHPs arising from the four basal ligands with slightly distinct bond lengths and bond angles may roughly cancel one another. The signs of hyperfine structure constants are also theoretically determined for both complexes.