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Solvent-dependent Ln(III) clusters assembled by immobilization of CO2 in air: zero-field single-molecule magnets and
Cai-Ming Liu1, Xiang Hao1, Zhao-Bo Hu2
1Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory for Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. cmliu@iccas.ac.cn.
Abstract:
The automatic fixation of CO2 in air played a key role in the construction of Dy(III) single-molecule magnets (SMMs) and Gd(III) magnetic refrigeration molecular materials when Ln(III)Cl3 (Ln = Dy and Gd) was reacted with a new hydrazone Schiff base ligand {H2L = (E)-N'-(4-fluoro-2-hydroxybenzylidene)pyrimidine-4-carbohydrazide}, which is condensed from pyrimidine-4-carbohydrazide and 4-fluorosalicylaldehyde. Surprisingly, the small difference in methanol and ethanol solvents leads to dramatic changes in the structures of these Ln(III) cluster complexes. When methanol and ethanol participated in the reaction, a trapezoidal pyramid Dy(III) pentanuclear cluster [Dy5L5(OH)2(CO3)(O2COMe)(MeOH)3(H2O)]·3MeOH·3.5H2O (1) and a triangular prism Dy(III) hexanuclear cluster [Dy6L6(CO3)2(EtOH)2(H2O)2Cl2]·6EtOH (2) were obtained, respectively, and a tub-like Gd(III) octanuclear cluster [Gd8L8(CO3)4(MeOH)3(H2O)5]·12MeOH·3CH2Cl2·3.25H2O (3) and a trapezoidal pyramid Gd(III) pentanuclear cluster [Gd5L4(HL)(CO3)O(OH)(EtOH)5(H2O)2Cl]·EtOH·3H2O (4) were yielded, respectively. Notably, 1 contains not only the carbonate anion, but also the monomethyl carbonate anion as the bridging ligand, which are formed by immobilizing CO2 in air, while 2, 3 and 4 contain the carbonate bridging ligand only. Magnetic properties' investigations revealed that both 1 and 2 are zero-field SMMs, with Ueff/k values of 93.2 K and 133.5 K, respectively, while 3 and 4 show large magnetocaloric effects, with the largest -ΔSm values of 27.49 J kg-1 K-1 at 2.0 K for ΔH = 7 T for 3 and 27.58 J kg-1 K-1 at 2.5 K for ΔH = 7 T for 4.
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