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Temperature-controlled polymorphism of chiral CuII-LnIII dinuclear complexes exhibiting slow magnetic relaxation
A new family of 3d-4f dinuclear complexes derived from a chiral Schiff-base ligand, (R,R)-N,N?-bis(3-methoxysalicylidene)cyclohexane-1,2-diamine (H2L), has been synthesized and structurally characterized, namely, [Cu(L)Ln(NO3)3(H2O)] (Ln = Ce (1) and Nd (2)), [Cu(L)Sm(NO3)3]¡¤2CH3CN (3) and [Cu(L)Ln(NO3)3] (Ln = Eu (4), Gd (5 and 5?), Tb (6 and 6?), Dy (7 and 7?), Ho (8), Er (9) and Yb (10)). Structural determination revealed that these complexes are composed of two diphenoxo-bridged CuII-LnIII dinuclear clusters with slight structural differences. Complexes 1, 2 and 4-7 crystallize in the chiral space group P1, and the space group of 3 is P21, while the other six complexes (5?-7? and 8-10) are isomorphous and each of them contains two slightly different CuII-LnIII dinuclear clusters in the asymmetric unit with the chiral space group P21. Magnetic investigations showed that ferromagnetic couplings between the CuII and LnIII ions exist in 5-7 and 5?-7?. Moreover, the alternating current (ac) magnetic susceptibilities of 6, 6?, 7 and 7? showed that both the in-phase (chi?) and out-of-phase (chi??) are frequency- and temperature-dependent with a series of frequency-dependent peaks for the chi??, which being typical features of field-induced slow magnetic relaxation phenomena. For 8, a frequency dependent chi? with peaks but chi?? without peaks appeared; however, the compound displays field-induced slow magnetic relaxation behavior. Furthermore, no obvious frequency-dependent ac signal was observed in 9 owing to the absence of the easy-axis anisotropy. More significantly, we observed the temperature-controlled reversible conversion from one chiral single-crystal (5-7) to another chiral single-crystal (5?-7?) exhibiting slow magnetic relaxation.
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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI