Mn-Fe Heterometallic Compounds within Hydrogen-Bonded Supramolecular Networks Promoted by an [Fe(CN)(CNH)] Building Block Structural and Magnetic Properties
Abstract
The reaction of [Fe(CN)] and [Mn(acacen)] (Hacacen = N, N'-bis(acetylacetone)ethylenediamine) building units in the presence of supramolecular cations, [(F-Anil)(18-crown-6)] (F-Anil = 3-fluoroanilinium) or [(Me-F-Anil)(18-crown-6)] (Me-F-Anil = 3-fluoro-4-methylanilinium), affords two new bimetallic compounds, [(F-Anil)(18-crown-6)][Mn(acacen)Fe(CN)(CNH)]·MeOH (1) and [(Me-F-Anil)(18-crown-6)][Mn(acacen)(MeOH)Fe(CN)(CNH)]·MeOH (2), respectively. Compound 1 exhibits a one-dimensional topology, while compound 2 is a dinuclear discrete system due to the coordination of a MeOH molecule at the axial position of the [Mn(acacen)] unit. For both systems, the acidity of the corresponding supramolecular cation triggers the protonation of the Fe moiety as [Fe(CN)(CNH)]. Moreover, the resulting -CNH ligand induces hydrogen bonding interactions connecting the chains for 1 or the molecules for 2 into higher dimensional supramolecular networks. Magnetic properties of compounds incorporating these [Fe(CN)(CNH)] building blocks were, for the first time, thoroughly investigated, indicating a three-dimensional antiferromagnetic order of single-chain magnets for 1 and an antiferromagnetically interacting S = 3/2 spin ground state for 2.