Influence of Magnetic Interactions and Single-Ion Anisotropy on Magnetic Relaxation within a Family of Tetranuclear Dysprosium Complexes.

Six tetranuclear DyIII complexes [Dy4(L)2(CH3OH)3(NO3)3]·3NO3·2H2O (1a), [Dy4(L)2(CH3OH)2(SCN)4(OCH3)2]·2CH3OH·2H2O (1b), {[Dy4(L)2(CH3OH)(SCN)6(CH3CN)]·3CH3OH·4CH3CN}2 (2a), [Dy4(L)2(CH3OH)2(SCN)6]·6CH3OH·2H2O (2b), [Dy4(L)2(CH3OH)2(SCN)4(OCH3)2]·5CH3OH·2H2O (3a), and [Dy4(L)2(CH3OH)(SCN)5(H2O)2]·SCN·4CH3OH·2H2O (3b) were structurally and magnetically characterized. The Dy1/Dy2 centers in these complexes are eight-coordinate and submitted to pseudo- D4d symmetry environments. It is noteworthy that the modulation of coordination terminal around Dy1/Dy2 centers induces distinct magnetic relaxation processes, switching from single relaxation (1b) to two-step relaxation (2b). All complexes show significant zero-field single-molecule magnet (SMM) properties with the exception of 3b, which only features the slow magnetic relaxation behavior under a zero dc field. Ab initio calculations substantiate that the excellent SMM property of complex 1b should mainly profit from strong ferromagnetic interactions between the individual DyIII ions, while different single-ion magnetism results in better SMM property of complex 3a than that of 3b.