The Nature of the Bridging Anion Controls the Single-Molecule Magnetic Properties of DyX4M 12-Metallacrown-4 Complexes

Thaddeus T Boron 3rd; Jacob C Lutter; Connor I Daly; Chun Y Chow; Andrew H Davis; Arunpatcha Nimthong-Roldán; Matthias Zeller; Jeff W Kampf; Curtis M Zaleski; Vincent L Pecoraro

doi:10.1021/acs.inorgchem.6b01832

The Nature of the Bridging Anion Controls the Single-Molecule Magnetic Properties of DyX₄M 12-Metallacrown-4 Complexes

Inorg Chem. 2016 Oct 17;55(20):10597-10607. doi: 10.1021/acs.inorgchem.6b01832. Epub 2016 Oct 5.

Authors

Affiliations

¹ Department of Chemistry, Slippery Rock University , Slippery Rock, Pennsylvania 16057, United States.
² Department of Chemistry, Shippensburg University , Shippensburg, Pennsylvania 17257-2200, United States.
³ Department of Chemistry, University of Michigan , Ann Arbor, Michigan 48108-1005, United States.
⁴ Department of Chemistry, Youngstown State University , Youngstown, Ohio 44555-0001, United States.

PMID: 27704795
DOI: 10.1021/acs.inorgchem.6b01832

Abstract

A family of DyX₄M(12-MC_Mn^III(N)shi-4) compounds were synthesized and magnetically characterized (X = salicylate, acetate, benzoate, trimethylacetate, M = Na^I or K^I). The bridging ligands were systematically varied while keeping the remainder of the MC-geometry constant. The type of monovalent cation, necessary for charge balance, was also altered. The dc magnetization and susceptibility of all compounds were similar across the series. Regardless of the identity of the countercation, the Dy(Hsal)₄M 12-MC-4 compounds were the only compounds to show frequency-dependent ac magnetic susceptibility, a hallmark of single-molecule magnetism. This indicates that the nature of the bridging ligand in the 12-MC_Mn^III(N)shi-4 compounds strongly affects the out-of-phase magnetic properties. The SMM behavior appears to correlate with the pK_a of the bridging ligand.