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The in situ hydrothermal reaction of CuI, NaN 3 and 4-(1H-imidazol-1-yl)benzonitrile leads to a new three-dimensional pillared-layer Cu(I)-MOF, [Cu 2 ( μ 3 -I)( μ 5 -IPT)] n ( 1 ) (HIPT = 5-[4-(imidazol-1-yl)phenyl]tetrazolate). Interestingly, the structure of 1 exhibits an unprecedented binodal (4, 8)-connected three-dimensional self-penetrating framework first constructed from [Cu 4 I 2 ] 2 + cationic clusters as 8-connected nodes and in situ generated IPT ligands as 4-connected nodes. Moreover, 1 is strongly luminescent with green emission ( λ em = 545 nm) in the solid-state. [ABSTRACT FROM AUTHOR]

An unprecedented self-penetrating Cu(I)-MOF was synthesized. Interestingly, Complex 1 exhibits a novel two-level hierarchical entangled system with a new (7 3 )(6 6 .7 4 )(6 6 .7 3 .8) topology first constructed from the rare meso -helical ladder and layer via inclined polycatenation, and also shows strong green emission in the solid-state and highly luminescent sensing for nitrobenzene. [ABSTRACT FROM AUTHOR]