Switching on single-molecule magnet properties of homoleptic sandwich tris(pyrazolyl)borate dysprosium(iii) cations via intermolecular dipolar coupling

Dimitris I Alexandropoulos; Kuduva R Vignesh; Haomiao Xie; Kim R Dunbar

doi:10.1039/c9dt00597h

Switching on single-molecule magnet properties of homoleptic sandwich tris(pyrazolyl)borate dysprosium(iii) cations via intermolecular dipolar coupling

Dalton Trans. 2019 Jul 16;48(28):10610-10618. doi: 10.1039/c9dt00597h.

Authors

Dimitris I Alexandropoulos¹, Kuduva R Vignesh¹, Haomiao Xie¹, Kim R Dunbar¹

Affiliation

¹ Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA. dunbar@chem.tamu.edu.

PMID: 31225555
DOI: 10.1039/c9dt00597h

Abstract

Two new homoleptic DyIII compounds [Dy(TpMe2)2][DyCl3(TpMe2)]·CH2Cl2 (1) and [Dy(TpMe2)2]I (3) as well as a heteroleptic (NMe4)[DyCl3(TpMe2)] (2) (TpMe2 = tris(3,5-dimethylpyrazolyl)borate) species are reported. Magnetic studies revealed that 1 is a single-molecule magnet (SMM) with an energy barrier of Ueff = 80.7 K with τ0 = 6.2 × 10-7 s under a zero applied field. Compound 3 exhibits a Ueff of 13.5 K with τ0 = 1.6 × 10-6 s under a 0.08 T applied field. Ab initio CASSCF + RASSI-SO calculations were performed to further investigate the magnetic behavior of complexes 1-3. The results support experimental magnetic data for 1 and 3 and indicate that an intermolecular dipolar interaction of (zJ = -0.1 cm-1) is responsible for the SMM behavior of 1.