Field-Induced Single-Ion Magnet Behavior in Nickel(II) Complexes with Functionalized 2,2':6'-2″-Terpyridine Derivatives: Preparation and Magneto-Structural Study.

Two mononuclear nickel(II) complexes of the formula [Ni(terpyCOOH)2](ClO4)2∙4H2O (1) and [Ni(terpyepy)2](ClO4)2 MeOH (2) [terpyCOOH = 4'-carboxyl-2,2':6',2″-terpyridine and terpyepy = 4'-[(2-pyridin-4-yl)ethynyl]-2,2':6',2″-terpyridine] have been prepared and their structures determined by single-crystal X-ray diffraction. Complexes 1 and 2 are mononuclear compounds, where the nickel(II) ions are six-coordinate by the six nitrogen atoms from two tridentate terpy moieties. The mean values of the equatorial Ni-N bond distances [2.11(1) and 2.12(1) Å for Ni(1) at 1 and 2, respectively, are somewhat longer than the axial ones [2.008(6) and 2.003(6) Å (1)/2.000(1) and 1.999(1) Å (2)]. The values of the shortest intermolecular nickel-nickel separation are 9.422(1) (1) and 8.901(1) Å (2). Variable-temperature (1.9-200 K) direct current (dc) magnetic susceptibility measurements on polycrystalline samples of 1 and 2 reveal a Curie law behavior in the high-temperature range, which corresponds to magnetically isolated spin triplets, the downturn of the χMT product at lower temperatures being due to zero-field splitting effects (D). Values of D equal to -6.0 (1) and -4.7 cm-1 (2) were obtained through the joint analysis of the magnetic susceptibility data and the field dependence of the magnetization. These results from magnetometry were supported by theoretical calculations. Alternating current (ac) magnetic susceptibility measurements of 1 and 2 in the temperature range 2.0-5.5 K show the occurrence of incipient out-phase signals under applied dc fields, a phenomenon that is characteristic of field-induced Single-Molecule Magnet (SMM) behavior, which herein concerns the 2 mononuclear nickel(II) complexes. This slow relaxation of the magnetization in 1 and 2 has its origin in the axial compression of the octahedral surrounding at their nickel(II) ions that leads to negative values of D. A combination of an Orbach and a direct mechanism accounts for the field-dependent relation phenomena in 1 and 2.