Switching on single-molecule magnet properties of homoleptic sandwich tris(pyrazolyl)borate dysprosium(iii) cations via intermolecular dipolar coupling. Issue 28 (21st June 2019)

• Record Type: Journal Article
• Authors: Alexandropoulos, Dimitris I.; Vignesh, Kuduva R.; Xie, Haomiao; Dunbar, Kim R.
• Is Part Of: Dalton transactions. Volume 48:Issue 28(2019)
• Page Start: 10610
• Page End: 10618
• Publication Date: 2019-06-21
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt00597h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Two new compounds containing the sandwich-type [Dy(Tp Me2 )2 ] + moiety are reported. Magnetic data and ab initio calculations revealed that intermolecular dipolar interactions have a major impact on the SMM properties of the compounds. Abstract : Two new homoleptic Dy III compounds [Dy(Tp Me2 )2 ][DyCl3 (Tp Me2 )]·CH2 Cl2 (1 ) and [Dy(Tp Me2 )2 ]I (3 ) as well as a heteroleptic (NMe4 )[DyCl3 (Tp Me2 )] (2 ) (Tp Me2 = tris(3, 5-dimethylpyrazolyl)borate) species are reported. Magnetic studies revealed that1 is a single-molecule magnet (SMM) with an energy barrier of U eff = 80.7 K with τ 0 = 6.2 × 10 −7 s under a zero applied field. Compound3 exhibits a U eff of 13.5 K with τ 0 = 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 complexes1–3 . The results support experimental magnetic data for1 and3 and indicate that an intermolecular dipolar interaction of ( zJ = −0.1 cm −1 ) is responsible for the SMM behavior of1 .