Polynuclear clusters can behave as single-molecule magnets (SMMs) if they possess a combination of a relatively large ground state spin (S) and Ising (easy-axis-type) magnetoanisotropy, i.e., negative zero-field splitting (D). In the last ten years, 3d-4f heterometallic complexes have been one of the fastest growing sources of SMMs due to the often large number of unpaired electrons and high anisotropy of lanthanide (Ln) ions, and often ferromagnetic coupling with transition metals. In the present study, we have explored and successfully achieved a triad of Mn/Ln cluster types from the use of 2-(hydroxymethyl)pyridine anion (hmp-), which had proven to be a versatile chelating and bridging ligand in previous work, and its two bulkier derivatives dimethyl-hmpH (dmhmpH) and diphenyl-hmpH (dphmpH). These three Mn/Ln families have been prepared under exactly the same conditions but differring in the size and electronic effects of the two substituents. This has allowed a systematic investigation of how targeted modification of chelates can affect the structural identities and magnetochemical properties of the obtained Mn/Ln complexes.

Structural and magnetic characterization Mn/Ln (Ln = Gd, Tb, Dy, Ho) single-molecule magnet clusters from the use of 2-(hydroxymethyl)pyridine and its bulkier derivatives

245th National Meeting (2013)

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