Construction of Zeolite-Like Cluster Organic Frameworks from 3d-4d/3d-3d Heterometallic Supertetrahedral Secondary Building Units: Syntheses, Structures, and Properties

Two zeolite-like cluster organic frameworks based on Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd4Cu6(L)(4)(H2O)(18)](-)(Ac)(9)center dot DMA center dot 3H(2)O (1), and Cu[Mn4Cu6(L)(4)(Ac)(3)(H2O)(12)](Ac)(6)center dot CH3CN center dot 13H(2)O (2), where H3L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH3COO-, DMA=N,N'-dimethylacetamide. Single-crystal X-ray structural analysis reveals that both 1 and 2 exhibit 3-dimensional zeolite-like architectures with similar 4-connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite-like cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied.