Construction of Zeolite-Like Cluster Organic Frameworks from 3 d-4 d/3 d-3 d 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[Cd4 Cu6 (L)4 (H2 O)18 ](Ac)9 ⋅DMA⋅3 H2 O (1), and Cu[Mn4 Cu6 (L)4 (Ac)3 (H2 O)12 ](Ac)6 ⋅CH3 CN⋅13 H2 O (2), where H3 L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH3 COO- , 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.