Chiral Dy(III) Fluorescent Single-Molecule Magnet Based on an Achiral Flexible Ligand

Abstract

A novel multi-channel barcode module was developed by using chiral co-crystals which contain field-induced SMM behavior and different emission bands. The chiral co-crystals [Zn(H2L)Dy(DBM)2]4(ClO4)4⋅9CH3OH⋅H2O (1a) and [Zn(H2L)Dy(DBM)2]4(ClO4)4⋅8CH3OH⋅0.5H2O (1b) (H4L = 2,2′-[1,2-ethanediylbis[(hydroxyethylimino)methylene]]bis[6-methoxy-4-methyl-phenol], HDBM = dibenzoylmethane) were obtained through one-pot reaction of ZnII and DyIII with the achiral ligands H4L and HDBM. X-ray single crystal diffraction and CD spectroscopy confirmed that they are enantiomers crystallized in P43 (1a) and P41 (1b), both consisting of two ∆-[Zn(H2L)Dy(DBM)2]+ cations, two Λ-[Zn(H2L)Dy(DBM)2]+ cations and four (ClO4)− anions. The presence of DyIII ions endow them with the property of field-induced slow magnetic relaxation. The relatively low energy barrier of 35.0(9) K for complex 1 may be due to the poor axiality of the ligand field caused by the long Dy-Ophenoxy bond lengths and the small Ophenoxy-Dy-Ophenoxy bond angles. Moreover, when the organic ligands H4L (λex = 350 nm) and DyIII (λex = 420 nm) are excited, different emission spectra are observed.