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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. [ABSTRACT FROM AUTHOR]

A series of dinuclear lanthanide(III) complexes having general formulae [Ln2L2(thd)4] ⋅ 2CH3CN {Ln=DyIII(1), TbIII(2), GdIII(3), ErIII(4)} were successfully synthesized using Schiff base (E)‐2‐((pyridin‐2‐ylmethylene)amino)phenol (LH) and co‐ligand 2,2,6,6‐Tetramethyl‐3,5‐heptanedione (Hthd). The single crystal XRD data shows that complexes possess a dinuclear planar [Ln2(μ2‐O)2]4+ core where phenolate oxygen atoms act as bridges between the two LnIII ions, and that the coordination sphere of LnIII with eight coordination has distorted trigonal dodecahedron geometry. The magnetic analysis shows complex 1 is a single molecule magnet having a zero‐field effective energy barrier (Ueff) of 54.02 K and relaxation time of τo=4.45×10−6 s. Field‐induced SMM behavior has been observed for 4 with an effective energy barrier of 26.9 K and τ0=2.4×10−9 s. CASSCF+RASSI‐SO calculations on 1, 2 and 4 provide deep insight regarding the electronic structure and single‐ion anisotropy of lanthanide ions. Further, using state‐of‐the‐art ab initio calculations, the nature of magnetic anisotropy and magnetic exchange interaction between the LnIII centers is analyzed to shed light on the magnetic dynamics of all the complexes 1–4. [ABSTRACT FROM AUTHOR]