Family of Chiral Zn-Ln (Ln = Dy and Tb) Heterometallic Complexes Derived from the Amine-Phenol Ligand Showing Multifunctional Properties.

A family of chiral 3d-4f heterometallic complexes, namely, ZnLn(,-L)(HO)) [Ln = Dy (), Tb ()], ZnLn(,-L)(HO) [Ln = Dy (), Tb ()], [ZnLn(,-L)(CO)(NO)]·2CHOH [Ln = Dy (), Tb ()], and [ZnLn(,-L)(CO)(NO)]·2CHOH [Ln = Dy (), Tb ()] {HL = cyclohexane-1,2-diylbis(azanediyl)bis(methylene)bis(2-methoxyphenol)}, has been synthesized and characterized. Crystal structure analysis reveals that complexes - are isostructural trinuclear clusters crystallized in chiral space group 22, and - are isostructural tetranuclear clusters crystallized in chiral space group 1. Interestingly, the adjacent [ZnLn] units within the tetranuclear cluster in - are bridged by two carbonate anions incorporation of CO from air. Magnetic measurements indicate that complexes and exhibit field-induced single-molecule magnet behavior with energy barriers () of 22.46 and 38.70 K (or 41.87 K), respectively. Complex displays typical SMM behavior with = 19.61 K under zero dc field, while for complex , no obvious out-of-phase signals are observed even under 2 kOe dc field, the absence of SMM behavior. The solid-state luminescence studies reveal that all complexes display the characteristic fluorescence emission of lanthanide ions. Furthermore, the Kurtz-Perry measurements reveal these complexes are potential nonlinear optical materials.