Self-Assembly Bifunctional Tetranuclear Ln 2 Ni 2 Clusters: Magnetic Behaviors and Highly Efficient Conversion of CO 2 under Mild Conditions.

A series of heterometallic tetranuclear clusters, Ln 2 Ni 2 (NO 3 ) 4 L 4 (μ 3 -OCH 3 ) 2 ·2(CH 3 CN) (Ln = Gd( 1 ), Tb( 2 ), Dy( 3 ), Ho( 4 ), Er( 5 ); HL = methyl 3-methoxysalicylate), were synthesized solvothermally. The intramolecular synergistic effect of two metal centers of Ln(III) and Ni(II) and the exposed multimetallic sites serving as Lewis acid activators greatly increase the efficiency of the CO 2 conversion, and the yield for cluster 3 can be achieved at 96% at atmospheric pressure and low temperature. In particular, the self-assembly multimetal center with polydentate ligand shows good generality and enhanced recyclability. The design of such 3d-4f heterometallic clusters provides an effective strategy for the conversion of CO 2 under greener conditions. Meanwhile, magnetic investigations indicate that cluster 1 is a good candidate for magnetic refrigerant materials with a relatively large magnetocaloric effect (MCE) (-Δ S m = 28.5 J kg -1 K -1 at 3.0 K and 7.0 T), and cluster 3 shows single-molecular magnet behavior under zero dc field. Heterometallic clusters with special magnetic properties and good catalytic behavior for the conversion of CO 2 are rare. Thus, they are potential bifunctional materials applied in practice.