Four helical coordination polymers, [Cd(anti-bime)(1,3-pda)]
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(1), [Cd(gauche-bime)(1,4-pda)]
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(2), [Co(anti-bime)(1,2-pda)]
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(3), and [Co(gauche-bime)(1,4-pda)]
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(4), have been solvothermally prepared by the assembly of mixed flexible ligands, bime and 1,3-H2pda, 1,4-H2pda, 1,2-H2pda with Cd(NO3)2·4H2O and Co(NO3)2·6H2O, respectively (bime = 1,2-bis(imidazol-1′-yl)ethane, 1,3-H2pda = 1,3-phenylenediacetic acid, 1,4-H2pda = 1,4-phenylenediacetic acid, 1,2-H2pda = 1,2-phenylenediacetic acid). Single-crystal X-ray diffraction analyses reveal that all of the complexes possess helical structures owing to the use of mixed flexible ligands; the conformations of flexible bime are entirely different, anti-bime occurs in 1 and 3, while gauche-bime occurs in 2 and 4. The fluorescent properties of 1 and 2 suggest that the intense broad photoluminescence emission at 387 nm for 1 and 389 nm for 2, 3, and 4 exhibit similar weak antiferromagnetic coupling between the Co2+ centers.