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Anion Effects on the Structural and Magnetic Properties of a Series of Trinuclear Cu II –Ln III –Cu II Complexes

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Two series of heterometallic Cu II 2 Ln III complexes, ([Cu 2 Ln( H 4 L ) 2 (MeOH) 2 Br](MeOH) 4 (Et 2 O)(Br 2 ), where Ln = Y ( 1 ), Gd ( 2 ), Er ( 3 ), Tb ( 4 )), and ([Cu 2 Ln( H 4 L ) 2 (MeOH) 2 Cl 2 ](MeOH) 4 (Et 2 O)Cl, where Ln = Y (5), Gd (6), Er (7), Tb (8), and H 6 L = ( N, N ′-bis(2,3,4-trihydroxybenzylidene)-1,2-phenylenediamine), were designed, synthesized, and characterized through X-ray and magnetic analyses. X-ray analysis revealed that the bromide containing complexes 1 – 4 possessed identical supramolecular arrangements, crystallizing in layers of 2D sheets, while chloride containing complexes 5 – 8 formed a 3D supramolecular lattice possessing an additional π–π stacking interaction per complex. DC magnetic susceptibility measurements showed that complexes 3 and 7 exhibited antiferromagnetic coupling between copper and erbium centers while the gadolinium ( 2 and 6 ) and terbium ( 4 and 8) containing complexes displayed ferromagnetic Cu─Ln coupling upon cooling. AC magnetic susceptibility measurements revealed that complexes 4 and 8 also displayed zero-field SMM behavior with U eff = 17.8 and 16.0 K, respectively. The larger bromide anion in complex 4 aids in the isolation of the magnetic centers, resulting in a U eff value higher than that of the chloride analogue.

Source: ACS Omega

DOI: 10.1021/acsomega.5c01224