A family of chiral 3d-4f heterometallic complexes, namely, [Zn(2)Ln(R,R-L)(2)(H2O)(4)](ClO4)(3)) [Ln = Dy (1), Tb (3)], [Zn(2)Ln(S,S-L)(2)(H2O)(4)](ClO4)(3) [Ln = Dy (2), Tb (4)], [Zn(2)Ln(2)(R,R-L)(2)(CO3)(2)(NO3)(2)]center dot 2CH(3)OH [Ln = Dy (5), Tb (7)], and [Zn(2)Ln(2) (S,S-L)(2)(CO3)(2)(NO3)(2)]center dot 2CH(3)OH [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 C2(2)2(1), 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 (U-eff) of 22.46 and 38.70 K (or 41.87 K), respectively. Complex 5 displays typical SMM behavior with U-eff = 19.61 K under zero dc field, while for complex 7, 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.