Neutral Low-Dimensional Assemblies of a Mn(III) Schiff Base Complex and Octacyanotungstate(V): Synthesis, Characterization, and Magnetic Properties

• Published in: Magnetochemistry 2017-06, Vol.3 (2), p.16
• Main Authors: Majcher, Anna M., Pilet, Guillaume, Mironov, Vladimir S., Vostrikova, Kira E.
• Format: Article
• Language: English
• Subjects: Antiferromagnetism; Chemical Sciences; Chemical synthesis; Coordination chemistry; Coordination compounds; Coupling (molecular); Cristallography; Crystal structure; Crystallography; Cyanides; Diffusion rate; Ferromagnetism; Imines; Iron constituents; Ligands; Localization; Magnetic materials; Magnetic properties; Magnets; Reagents; Self-assembly; Water chemistry
• ISSN: 2312-7481; 2312-7481
• DOI: 10.3390/magnetochemistry3020016

Two novel low-dimensional molecular magnetic materials were prepared by the self-assembly of 3d- and 5d-metal complexes. These are the first neutral heterobimetallic cyanobridged compounds involving one anisotropic Mn(III) Schiff base complex and one octacyanotungstate(V) per molecular unit. A slow diffusion of the constituents’ solutions leads to the formation of the 0D crystalline complex 1, due to coordination of a water molecule to the Mn center, which prevents polymer formation. A rapid mixing of reagents results in the precipitation of the microcrystalline powder of complex 2, which based on the totality of experimental data, possesses a 1D polymeric structure. The magnetic studies have shown that antiferromagnetic exchange interactions prevail in 1 (J/kB = −13.1(7) K, D = −3.0(1.3) K, zJ' = −0.16(20) K and gav = 2.00(1)); while the presence of the significant intramolecular Mn(III)–W(V) ferromagnetic coupling through cyanide bridge is characteristic for 2 (J/kB = 46.1(5) K, gMn = 2.11(3), fixed gW = 2.0). Due to the weak interchain interactions, zJ′/kB = −0.8(2) K, and compound 2 is a metamagnet with the Néel temperature of 9.5 K undergoing a spin-flip transition at 2 kOe. The slow magnetization dynamics of 2 were investigated at a DC field of 0 and 2 kOe, giving the values of τ0 32(15) and 36(15) ps, respectively, well within the range typical for single-chain magnets (SCMs). The respective ∆τ/kB values were 48.4(1.2) and 44.9(1.0) K.