Three Linear Trinuclear Zinc(II) Complexes with Acenaphthenequinone Dioxime and the Ancillary Ligand 2‐Amino‐2‐methyl‐1‐propanol in Different Coordination Modes

Abstract

Three linear trinuclear complexes [Zn3L3(HAMP)2]·2MeOH (1), [Zn3L3(HAMP)2]·2DMF·2EtOH (2), and [Zn3L3(HAMP)2]·DMF·EtOH (3) were separated from the reactions of ZnII salts with acenaphthenequinone dioxime (H2L) and 2‐amino‐2‐methyl‐1‐propanol (HAMP) under different reaction conditions. They were structurally characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffractional analysis. All of them present a similar linear trinuclear skeleton with the three ZnII ions linked by three L2– ligands. The coordination arrangements of their terminal ZnII ions and the coordination modes of the two HAMP ancillary ligands are different. 1 has two five‐coordinate bipyramidal terminal ZnII ions with the two HAMP molecules chelated to the two terminal ZnII ions, while the two terminal metal ions in 3 are both tetracoordinate in tetrahedral arrangements with the two HAMP molecules in monodentate coordination modes. However, 2 shows different coordination modes (bipyramidal and tetrahedral) for the two terminal ZnII ions with the two HAMP molecules in chelated and monodentate coordination modes, respectively. Their luminescent properties were also investigated.

New Dioximes as Bridging Ligands in 3d/4f-Metal Cluster Chemistry: One-Dimensional Chains of Ferromagnetically Coupled {Cu6Ln2} Clusters Bearing Acenaphthenequinone Dioxime and Exhibiting Magnetocaloric Properties

“…All manipulations were performed under aerobic conditions using chemicals and solvents as received. Acenaphthenequinone dioxime (acndH 2 ) was prepared and characterized according to a literature method described elsewhere. − The lanthanide­(III) acetylacetonate precursors, Ln­(acac) 3 ·H 2 O (Ln = Gd, Dy), were synthesized as previously reported …”

“…The ligand acndH 2 has only been used in homometallic 3dmetal cluster chemistry for the synthesis of a family of {Zn 3 } linear clusters with luminescent properties 45 and a series of antiferromagnetically coupled Mn III and Mn II/III clusters. 46 We herein report the synthesis, structures, and detailed magnetic studies of a new family of {Cu II 6 Ln III 2 } clusters which extend their structures into covalently linked one-dimensional (1-D) chains; the compounds are predominantly ferromagnetically coupled, and the {Cu 6 Gd 2 } n analogue shows magnetocaloric properties.…”