Synthesis, crystal structures and magnetic properties of cyanide-bridged macrocyclic complexes

Three cyanide-bridged dodecanuclear macrocyclic wheel-like complexes [Cr(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (1), [Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H2O (2) and [Co(bpmb)(CN)2]6[Mn(5-Clsalpn)]6·24H2O·8CH3CN (3) [bpmb2−= 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate dianion; 5-Brsalpn2− = N,N′-propylenebis(5-bromosalicylideneaminato) dianion; 5-Clsalpn2− = N,N′-propylenebis(5-chlorosalicylideneaminato) dianion] have been synthesized and their crystal structures and magnetic properties have been investigated. The three compounds are structurally isomorphous and consist of alternating Mn(III)-Schiff base cations and [M(bpmb)(CN)2]− anions, generating cyanide-bridged nanosized dodecanuclear macrocyclic structures with an approximate diameter of 2 nm. The study of the magnetic properties of complex 1 reveals an antiferromagnetic interaction between the Cr(III) and Mn(III) ions through the cyanide bridges. A best-fit to the magnetic susceptibility of the complex leads to a magnetic coupling constant of JCrMn = −2.65(6) cm−1 on the basis of a one-dimensional alternating chain model with the Hamiltonian \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$ H = - J_{CrMn} \sum\limits_{i = 0}^N {S_i \cdot S_{i + 1} } $$\end{document}.