Crossover from Antiferromagnetic to Ferromagnetic Exchange Coupling in a New Family of Bis-(μ-phenoxido)dicopper(II) Complexes: A Comprehensive Magneto–Structural Correlation by Experimental and Theoretical Study

[Image: see text] Five neutral bis(μ-phenoxido)dicopper(II) complexes, [Cu(2)(L(Me,Me,Me))(2)] (1), [Cu(2)(L(Me,Me,Et))(2)]·CH(2)Cl(2) (2), [Cu(2)(L(i-Pr,i-Pr,i-Pr))(2)]·2H(2)O (3), [Cu(2)(L(t-Bu,Me,i-Pr))(2)] (4), and [Cu(2)(L(t-Bu,t-Bu,i-Pr))(2)]·H(2)O (5) have been synthesized and characterized by single-crystal X-ray diffraction analyses, magnetic studies, and density functional theory (DFT) calculations, in which the ligands [H(2)L(Me,Me,Me) = N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-N′,N′-dimethylethylene-1,2-diamine, H(2)L(Me,Me,Et) = N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-N′,N′-dimethylethylene-1,2-diamine, H(2)L(i-Pr,i-Pr,i-Pr) = N,N-bis(2-hydroxy-3,5-diisopropylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine, H(2)L(t-Bu,Me,i-Pr) = N,N-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine, and H(2)L(t-Bu,t-Bu,i-Pr) = N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)-N′,N′-diisopropylethylene-1,2-diamine] contain the same [O,N,N,O]-donor atoms combination but differ in substituents at phenol rings and at an amino nitrogen atom. The effect of these remote substituents on the nature of exchange coupling interactions (ferromagnetic vs antiferromagnetic) between the copper(II) ions has been investigated. The average Cu–O–Cu angle, Cu–O–Cu–O torsion angle, and Cu···Cu separation in 1–5 are varied systematically by these remote ligand substituents in the range 98.6–83.3°, 26.0–46.5°, and 2.982–2.633 Å, respectively. As a result, the intramolecular spin–spin coupling in these complexes are changing gradually from a strong antiferromagnetic (J = −395 cm(–1), where Ĥ = −JŜ(1)Ŝ(2)) to a moderate ferromagnetic (J = +53.2 cm(–1)) regime. The crossover angle at which the magnetic interaction changes from antiferromagnetic to ferromagnetic (J = 0) is determined to be ca. 87° for this series of dicopper(II) complexes. DFT calculations support the experimentally determined crossover angle and disclose various magneto–structural correlations in the series 1–5.