From tetranuclear cluster with single-molecule-magnet behavior to 1D alternating spin-canting chain in a Fe(III)–Mn(III) bimetallic system

• Cyano-bridged tetranuclear or chain was synthesized via rational design.
• The tetranuclear cluster shows dominant ferromagnetic interaction and SMM behavior.
• The zigzag chain presents dominant antiferromagnetic behavior and spin-canting.

A tetranuclear cluster and an alternating zigzag chain were synthesized via rational assembly of the same cyanometalate building blocks with different Mn(III) Schiff bases possessing varying proportions of sterically hindered groups causing steric hindrances. The tetranuclear cluster [(Tp*)Fe(CN)3]2[Mn(salen)]2·H2O [1; [(Tp*)Fe(CN)3]− [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl) borate], salen = N,N′-ethylenebis(salicylideneiminato) dianion] was formed with Schiff bases possessing smaller steric hindrances, whereas the one-dimensional alternating zigzag chain {[(Tp*)Fe(CN)3Mn(salcyen)]·2CH3OH·H2O}n [2; salcyen = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion] was formed with Schiff bases possessing larger steric hindrances. Magnetic measurements revealed that 1 exhibits single-molecule-magnet behavior with dominant ferromagnetic interactions, whereas 2 exhibits spin-canting behavior with dominant antiferromagnetic interactions.

One tetranuclear cluster and one alternating zigzag chain were synthesized via directional assembly of metallocyanates with Mn(III) Schiff bases possessing different steric hindrances. Magnetic measurements revealed that the tetranuclear cluster exhibits SMM behavior with dominant ferromagnetic interactions, whereas the 1D chain presents spin-canting behavior with dominant antiferromagnetic interactions.Figure optionsDownload as PowerPoint slide