Dinuclear alkoxo-bridged copper(II) coordination polymers: Syntheses, structural and magnetic properties

The alkoxo-bridged dinuclear copper(II) complexes [Cu2(ap)2(NO2)2] (1), [Cu2(ap)2(C6H5COO)2] (2) and [Cu2(ap)2μ-1,3-C6H4(COO)2(dmso)2]·dmso (3) (ap = 3-aminopropanolato and dmso = dimethyl sulfoxide) have been synthesized via self-assembly from copper(II) perchlorate, 3-aminopropanol as main chelating ligand and nitrite and isophthalate anions as spacers and benzoate anion as auxiliary ligand. Complexes 1 and 3 crystallize as 2D and 1D coordination polymers, respectively, and their structures consist of dinuclear [Cu2(ap)2]2+ units connected with nitrite and isophthalate ligands. The adjacent dinuclear units of 2 and 1D polymers of 3 are further connected by hydrogen bonds resulting in the formation of 2D layers. The variable temperature crystallographic measurements of 1 at 100, 173 and 293 K indicate the static Jahn–Teller distortion with librational disorder in the nitrite group. Experimental magnetic studies showed that complexes 1–3 exhibit strong antiferromagnetic couplings. The values of the magnetic exchange coupling constant for 1–3 are well reproduced by the theoretical calculations.

Graphical abstractThe alkoxo-bridged dinuclear copper(II) complexes [Cu2(ap)2(NO2)2] (1), [Cu2(ap)2(C6H5COO)2] (2) and [Cu2(ap)2μ-1,3-C6H4(COO)2(dmso)2]·dmso (3) (ap = 3-aminopropanolato and dmso = dimethyl sulfoxide) have been synthesized and structurally characterized. The pseudo-Jahn–Teller distorted 4 + 1 + 1 coordination of dinuclear Cu(II) unit of 1 has been explored with variable temperature crystallographic measurements. The magnetic properties of complexes 1–3 have been investigated.Figure optionsDownload full-size imageDownload as PowerPoint slide