Binuclear Metal Complexes. XI. Substituent Effect upon Magnetisms of Binuclear Oxovanadium(IV) and Copper(II) Complexes of the Schiff Bases, 2,6-Bis[N-(2-hydroxy-5-substituted-phenyl)iminomethyl]-4-methylphenol

Binuclear oxovanadium(IV) and copper(II) complexes, M2(fsalap-R)(OMe) (R=H, CH3, Cl, and NO2) were synthesized and characterized, where H3fsalap-R denotes 2,6-bis[N-(2-hydroxy-5-substituted-phenyl)iminomethyl]-4-methylphenol and the metal ions are connected by the phenolic oxygen and a methanolate ion. The cryomagnetic properties of the complexes except Cu2(fsalap-NO2)(OMe) could be interpreted on the basis of the Bleaney-Bowers equation. It was found that the -2J values for the oxovanadium(IV) complexes increase in the order (VO)2(fsalap-CH3)(OMe) Cu2(fsalap-H)(OMe)>Cu2(fsalap-Cl)(OMe). These facts could be reasonably explained in terms of the difference in structures and spin-exchange mechanisms between the oxovanadium(IV) and the copper(II) complexes. (VO)2(fsalap-NO2)(OMe) showed a very strong antiferromagnetic spin-exchange interaction (−2J=545 cm−1) compared with the other...

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