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Two 3d transition metal mononuclear complexes, [(Fe L 2)(ClO4)2]2·CH3CN (1) and (Co L 2)(ClO4)2·2CH3CN (2), have been prepared from a rigid tetradentate bpybox (L = 6,6′-bis(2,5-dihydrooxazol-4-yl)-2,2′-bipyridine) ligand. Single crystal X-ray diffraction analyses together with the help of calculations show that both compounds are octa-coordinate. Direct current magnetic studies reveal their significant magnetic anisotropy. Impressively, field-induced relaxation of magnetism is observed in the two complexes and the apparent anisotropy barriers are 14.1 K for 1 and 21.6 K for 2, respectively. Theoretical calculations reveal that two Fe(II) centers in 1 have small negative D values of −4.897 and −4.825 cm−1 and relatively small E values of 0.646 and 0.830 cm−1, indicating a uniaxial magnetic anisotropy. In contrast, the D and E values in the Co(II) center of 2 are 46.42 cm−1 and 11.51 cm−1, featuring a rhombic anisotropy. This work demonstrates that field-induced slow magnetic relaxation in 3d transition metal complexes with high coordination numbers can be manipulated through rigid ligand design. [ABSTRACT FROM AUTHOR]

Two 3d transition metal mononuclear complexes, [(FeL 2 )(ClO 4 ) 2 ] 2 ·CH 3 CN (1) and (CoL 2 )(ClO 4 ) 2 ·2CH 3 CN (2), have been prepared from a rigid tetradentate bpybox (L = 6,6'-bis(2,5-dihydrooxazol-4-yl)-2,2'-bipyridine) ligand. Single crystal X-ray diffraction analyses together with the help of calculations show that both compounds are octa-coordinate. Direct current magnetic studies reveal their significant magnetic anisotropy. Impressively, field-induced relaxation of magnetism is observed in the two complexes and the apparent anisotropy barriers are 14.1 K for 1 and 21.6 K for 2, respectively. Theoretical calculations reveal that two Fe(II) centers in 1 have small negative D values of -4.897 and -4.825 cm -1 and relatively small E values of 0.646 and 0.830 cm -1 , indicating a uniaxial magnetic anisotropy. In contrast, the D and E values in the Co(II) center of 2 are 46.42 cm -1 and 11.51 cm -1 , featuring a rhombic anisotropy. This work demonstrates that field-induced slow magnetic relaxation in 3d transition metal complexes with high coordination numbers can be manipulated through rigid ligand design.