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Three polymers [Zn2(p‐CPIDA)(OH)]n (1), [Zn2(p‐HCPIDA)2(bipy)(H2O)4]·2H2O (2), and [Zn(m‐HCPIDA)(bipy)]n (3) [p/m‐H3CPIDA = N‐(4/3‐carboxyphenyl) iminodiacetic acid, bipy = 4, 4′‐bipyridine] were hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, X‐ray powder diffraction patterns (XPRD), FTIR spectroscopy, and fluorescence analyses. Compound 1 displays an interesting three‐dimensional framework consisting of novel paddle wheel Zn8O10C2 units, which are further linked by p‐CPIDA3– ligands with versatile coordination modes. In 2, the structural motifs formed by terminal p‐HCPIDA2– ligands and ZnII ions are bridged by ancillary bipy to give a zero‐dimensional Z‐shaped dimer. Compound 3 has an infinite zigzag chain linked by bipy, in which terminal m‐HCPIDA2– ligands alternately run along the chain like flags. Compounds 2 and 3 are further connected by hydrogen bonding and π···π stacking interactions to result in 3D supramolecular frameworks. Moreover, compounds 1–3 exhibit intense solid state fluorescent emissions at room temperature.
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