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Compounds with redox activities have appealing applications in catalytic, electronic and magnetic properties, but the redox inert of polyoxoniobates (PONbs) significantly limits their applications for a long time. In this work, we are able to integrate organophosphate and lanthanide cluster into PONb to create the first family of inorganic‐organic hybrid organophosphate‐Ln‐PONb composite clusters. These novel species not only present the first family of redox active PONbs that can be reduced to form long‐lived "heteropoly blues" under ambient conditions, but also a new photochromic system. More importantly, the analyses of the electronic configurations and photochromic properties for a series of designed proof‐of‐concept PONbs models allow us to discover a D‐f‐A electron transfer mechanism, that is, photoinduced electron is transferred from a photosensitive organophosphate electron donor (D) to the NbV electron acceptor (A) through the unoccupied 4 f‐orbitals of Ln (f). This work paves the way for developing diverse PONb‐based redox materials and expanding the possibility of the applications of PONbs in the redox chemistry. [ABSTRACT FROM AUTHOR]

Two unique heterometallic cluster organic frameworks, [Cd4MnIII4MnII6(Tri)4(CH3COO)14(μ4‐O)2(μ3‐O)2(H2O)2] Cd(H2O)2⋅9 H2O (1) and Cu[Cd5Cu6(Tri)4(CH3COO)9(H2O)4]2(CH3COO)3⋅24 H2O (2) (H3Tri=2‐(hydroxymethyl)‐2‐(pyridine‐4‐yl)‐1,3‐propanediol), have been successfully prepared by employing a bifunctional tripodal alcohol ligand as a structure‐directing agent. Crystal structure analyses reveal that 1 represents a rare example of frameworks constructed from Cd−Mn heterometallic chains, and 2 is the first heterometallic MOF based on highest‐nuclear Cd−Cu heterometallic cluster building blocks. Furthermore, the magnetic properties and gas adsorption abilities of 1 and 2 were systematically studied. [ABSTRACT FROM AUTHOR]

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 ⋅DMA ⋅3 H2O ( 1), and Cu[Mn4Cu6(L)4(Ac)3(H2O)12](Ac)6 ⋅CH3CN ⋅13 H2O ( 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. [ABSTRACT FROM AUTHOR]