A Family of {Cr(2)(III)Ln(2)(III)} Butterfly Complexes: Effect of the Lanthanide Ion on the Single-Molecule Magnet Properties

作者：Langley Stuart K^*; Wielechowski Daniel P; Chilton Nicholas F; Moubaraki Boujemaa; Murray Keith S

来源：Inorganic Chemistry, 2015, 54(21): 10497-10503.

DOI：10.1021/acs.inorgchem.5b01999

We report the synthesis of several heterometallic 3d-4f complexes which result from the replacement of the Dy-III ions in the [(Cr2Dy2III)-Dy-III(OMe)(2)(mdea)(2)(O2CPh)(4)(NO3)(2)] single-molecule magnet (SMM) by the trivalent Pr, Nd, Gd, Tb, Ho, and Er lanthanide ions. The parent {Cr2Dy2III} compound displayed an anisotropy barrier to magnetization reversal of 53 cm(-1), with magnetic hysteresis observed up to 3.5 K and with large coercive fields at low temperatures (2.7 T at 1.8 K). Magnetic studies for the new complexes revealed significantly different static and dynamic magnetic behavior in comparison to the parent {(Cr2Dy2III)-Dy-III} complex. When Ln(III) = Pr, a complete loss of SMM behavior is found, but when Ln(III) = Nd or Er, frequency-dependent tails in the out-of-phase susceptibility at low temperatures are observed, indicative of slow magnetic relaxation, but with very small anisotropy barriers and fast relaxation times. When Ln(III) = Tb and Ho, SMM behavior is clearly revealed with anisotropy barriers of 44 and 36 cm(-1), respectively. Magnetic hysteresis is also observed up to 2.5 and 1.8 K (0.003 T/s) for the Tb and Ho complexes, respectively. A large loss of the magnetization is, however, observed at zero-field, and as a result, the large coercivity which is present in the {Cr2Dy2} example is lost. The {Cr2Tb2} and {Cr2Ho2} complexes are rare examples of Tb- and Ho-based SMMs which reveal both slow relaxation in the absence of a static dc field (ac susceptibility) and open hysteresis loops above 1.8 K.

• 出版日期2015-11-2