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) (−ΔS 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.

The design and construction of high-nuclear lanthanide clusters with fascinating topology and functions have been an active area of research, however, the effective approach for obtaining high-nuclear lanthanide clusters with...

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A series of new Ln8 clusters [Ln8(acac)4(HL)4(L)2(μ3-O)4(C2H5O)4]·2C2H5OH·2CH2Cl2 (Ln(III) = Gd (1), Dy (2), and Ho (3); Hacac = acetylacetone and H2L = 2-hydroxy-benzoic acid (5-hydroxymethyl-furan-2-ylmethylene)-hydrazide) have been designed and constructed using a multiple coordination site Schiff base ligand (H2L) as  well  as a β-diketonate auxiliary ligand.  The structures, magnetic properties, and catalytic performance of clusters 1–3 have been studied. X-ray crystallography data revealed that clusters 1–3 possess similar structures with two chair-form Ln4 cores bridged by four μ3-O atoms. Clusters 1–3 display extensive and high solvent stability. Magnetic analysis exhibits that cluster 1 possesses a comparably large magnetocaloric effect (−ΔS m = 33.06 J kg–1 K–1 at 2.0 K and 7.0 T). AC susceptibility measurement suggests that cluster 2 exhibits single-molecule magnet behavior under zero-field conditions. What’s more, all clusters can effectively convert CO2 with epoxides. The highest yield is 98% at 70 °C 0.1 MPa catalyzed by 1. In addition, cluster 1 can be reused three times with a negligible loss of catalytic activity.

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