Tuning of Exchange Coupling and Switchable Magnetization Dynamics by Displacing the Bridging Ligands Observed in Two Dimeric Manganese(III) Compounds

Two Mn(III)-based dimers, [Mn2(bpad)2(CH3O)4]n (1) and [Mn2(bpad)2(pa)2]n·2H2O (2) (Hbpad = N3-benzoylpyridine-2-carboxamidrazone, H2pa = phthalic acid), have been assembled from a tridentate Schiff-base chelator and various anionic coligands. Noteworthily, compound 1 could be identified as a reaction precursor to transform to 2 in the presence of phthalic acid, resulting in a rarely structural conversion process in which the bridges between intradimer Mn(III) ions alter from methanol oxygen atom with μ2-O mode in 1 (Mn Mn distance of 3.046 Å) to syn-anti carboxylate in 2 (Mn Mn distance of 4.043 Å), while the Mn(III) centers retain hexa-coordinated geometries with independently distorted octahedrons in two compounds. The dc magnetic determinations reveal that ferromagnetic coupling between two metal centers with J = 1.31 cm-1 exists in 1, whereas 2 displays weak antiferromagnetic interactions with the coupling constant J of -0.56 cm-1. Frequency-dependent ac susceptibilities in the absence of dc field for 1 suggest slow relaxation of the magnetization with an energy barrier of 13.9 K, signifying that 1 features single-molecule magnet (SMM) behavior. This work presents a rational strategy to fine-tune the magnetic interactions and further magnetization dynamics of the Mn(III)-containing dinuclear units through small structural variations driven by the ingenious chemistry.