Family of dumbbell Ni4Ln2 (Ln = Pr, Sm, Eu, Gd, Tb, Ho, Er) complexes: syntheses, structures, luminescent and magnetic properties

Abstract

The synthesis and characterization of a family of heterometallic Ni₄Ln₂ complexes (Ln = Pr(1), Sm(2), Eu(3), Gd(4), Tb(5), Ho(6) and Er(7)) of the formula [Ni₂LnL¹L²(OH)(H₂O)]₂ are reported, where H₄L¹ is 3,3′-(1E,1′E)-(2,2′-(2-aminoethylazanediyl)bis(ethane-2,1-diyl)bis(azan-1-yl-1-ylidene))bis(methan-1-yl-1-ylidene)bis(2-hydroxybenzoic acid) and H₂L² is 3-formyl-2-hydroxybenzoic acid. The molecular structures of 1–7 were determined by single-crystal X-ray diffraction and reveal that they are isostructural. In all of these compounds, the six metal ions are held together to form a novel Ni₄Ln₂O₁₀ core and exhibit a relatively rare dumbbell-type structure. In these compounds, the Ni ions are in slightly distorted square-pyramidal or octahedral environments. An all-oxygen coordination environment (8O) is present around the central lanthanide ion, which is present in a distorted square antiprismatic geometry. The Ln–Ln and Ln–O_avg bond distances in 1–7 show a gradual reduction proceeding from 1 to 7, in accordance with the lanthanide contraction. The luminescent properties of all the compounds have been studied. The magnetic susceptibility analysis demonstrate antiferromagnetic interactions within complex 4.