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[Cd 4 Cu 6 (L) 4 (H 2 O) 18 ](Ac) 9 ⋅ DMA ⋅ 3 H 2 O ( 1 ), and Cu[Mn 4 Cu 6 (L) 4 (Ac) 3 (H 2 O) 12 ](Ac) 6 ⋅ CH 3 CN ⋅ 13 H 2 O ( 2 ), where H 3 L=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)‐1,3‐propanediol, Ac=CH 3 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.