Effect of diamagnetic Zn(II) ions on the SMM properties of a series of trinuclear ZnDy2 and tetranuclear Zn2Dy2 (LnIII = Dy, Tb, Gd)
Authors :- P. Shukla, I. Tarannum, S. Roy, A. Rajput, P. Lama, S. K. Singh, J. Kłak, J Lee, S. Das
Publication :- Dalton transactions, Apr.2024
To study the effect of diamagnetic ions on magnetic interactions, utilizing a compartmental ligand (Z)-2-(hydroxymethyl)-4-methyl-6-((quinolin-8-ylimino)methyl)phenol (LH2), two different series of ZnII–LnIII complexes, namely the trinuclear series of [DyZn2(L)2(μ2-OAc)2(CH3OH)2]·NO3·MeOH (1), [TbZn2(L)2(μ2-OAc)2(CH3OH)2]·NO3·5MeOH·H2O (2), and [GdZn2(L)2(μ2-OAc)2(CH3OH)2]·NO3·MeOH·CHCl3 (3) and the tetranuclear series of [Dy2Zn2(LH)4(NO3)4(μ2OAc)]·NO3·MeOH·H2O (4), [Tb2Zn2(LH)4(NO3)4(μ2-OAc)]·NO3·MeOH·2H2O (5), and [Gd2Zn2(LH)4(NO3)4(μ2-OAc)]·NO3·MeOH·2H2O (6), were synthesized. Trinuclear ZnII–LnIII complexes 1–3 consist of one LnIII ion sandwiched between two peripheral ZnII ions forming a bent type ZnII–DyIII–ZnII array with an angle of 110.64°. Tetranuclear ZnII–LnIII complexes 4–6 are basically a combination of two dinuclear moieties of [LnZn(LH)2(NO3)2]+ connected by one bidentate bridging acetate ion in μ2-OAc coordination mode. The detailed magnetic analysis reveals that complexes 1 and 4 are single molecule magnets having energy barriers of 34.98 K and 46.71 K with relaxation times (τ0) of 5.05 × 10−4 s and 5.24 × 10−4 s, respectively. Ab initio calculations were employed to analyze the magnetic anisotropy and magnetic exchange interaction between the ZnII and LnIII centers with the aim of gaining better insights into the magnetic dynamics of complexes 1–6.