Influence of ligand substitution and the solvent effect on the structures and magnetic properties of dinuclear Dy2 supramolecular architectures constructed with the bis-β-diketonate-Dy2 building block as a metalloligand

Abstract

Based on the bis-β-diketonate-Dy₂ metalloligand [Dy₂(pbth)₄]·2Et₃N (1, pbth = (3z,3′z)-4,4′-(1,3-phenylene)bis(1,1,1-trifluoro-4-hydroxybut-3-en-2-one)), six dinuclear complexes with eight-coordinated geometries were synthesized solvothermally through different capping N-donor coligands or solvent systems. These complexes are namely [Dy₂(pbth)₃(Phen)₂]·2C₂H₅OH (2), [Dy₂(pbth)₃(BPhen)₂]·2C₂H₅OH (3), [Dy₂(pbth)₃(Dppz)₂]·2C₂H₅OH (4), [Dy₂(pbth)₃(Dppz)₂]·2CH₃OH (4a), [Dy₂(pbth)₃(4-Dmbp)₂]·CH₃OH·C₂H₅OH (5) and [Dy₂(pbth)₃(5-Dmbp)₂]·CH₃OH (6) (Phen = 1,10-phenanthroline, BPhen = 4,7-diphenyl-1,10-phenanthroline, dppz = dipyrido [3,2-a:2′,3′-c] phenazine, 4-Dmbp = 4,4′-dimethyl-2,2′-bipyridyl, 5-Dmbp = 5,5′-dimethyl-2,2′-bipyridyl), respectively. In the synthetic processes of 2–6, one of four bis-β-diketonate ligands in the metalloligand is replaced by two capping N-donor coligands. The coordination geometries, metal distances and M–L–M torsion angles of the synthesized complexes are perceptibly fine-tuned by the modification of the capping N-donor coligands or the latticed solvent molecules. Systematic magnetic investigations indicate the different magnetic relaxation dynamics of 1–6. Complex 1 displays no characteristics of single-molecule magnets (SMMs), while complexes 2–6 exhibit SMM behaviours in the absence of a static magnetic field. Complexes 2 and 3 possess effective energy barriers (U_eff) of 110.18 (2) K and 133.21 (4) K, respectively. Theoretical analysis based on ab initio calculation provides some interpretations of experimental observation.