Family of Chiral ZnII–LnIII (Ln = Dy and Tb) Heterometallic Complexes Derived from the Amine–Phenol Ligand Showing Multifunctional Properties

A family of chiral 3d–4f heterometallic complexes, namely, [Zn2Ln(R,R-L)2(H2O)4](ClO4)3) [Ln = Dy (1), Tb (3)], [Zn2Ln(S,S-L)2(H2O)4](ClO4)3 [Ln = Dy (2), Tb (4)], [Zn2Ln2(R,R-L)2(CO3)2(NO3)2]·2CH3OH [Ln = Dy (5), Tb (7)], and [Zn2Ln2(S,S-L)2(CO3)2(NO3)2]·2CH3OH [Ln = Dy (6), Tb (8)] {H2L = cyclohexane-1,2-diylbis(azanediyl)bis(methylene)bis(2-methoxyphenol)}, has been synthesized and characterized. Crystal structure analysis reveals that complexes 1–4 are isostructural trinuclear clusters crystallized in chiral space group C2221, and 5–8 are isostructural tetranuclear clusters crystallized in chiral space group P1. Interestingly, the adjacent [ZnLn] units within the tetranuclear cluster in 5–8 are bridged by two carbonate anions via in situ incorporation of CO2 from air. Magnetic measurements indicate that complexes 1 and 3 exhibit field-induced single-molecule magnet behavior with energy barriers (Ueff) of 22.46 and 38.70 K (or 41.87 K), respectively. Complex 5 displays typical SMM behavior with Ueff = ...