Abstract: | Changing the pH value of a reaction system can result in polymers with very different compositions and architectures. Two new coordination polymers based on 1,1′‐[1,4‐phenylenebis(methylene)]bis(3,5‐dicarboxylatopyridinium) (L2?), namely catena‐poly[[[tetraaquacadmium(II)]‐μ2‐1,1′‐[1,4‐phenylenebis(methylene)]bis(3,5‐dicarboxylatopyridinium)] 1.66‐hydrate], {[Cd(C22H14N2O8)(H2O)4]·1.66H2O}n, (I), and poly[{μ6‐1,1′‐[1,4‐phenylenebis(methylene)]bis(3,5‐dicarboxylatopyridinium)}cadmium(II)], [Cd(C22H14N2O8)]n, (II), have been prepared in the presence of NaOH or HNO3 and structurally characterized by single‐crystal X‐ray diffraction. In polymer (I), each CdII ion is coordinated by two halves of independent L2? ligands, forming a one‐dimensional chain structure. In the crystal, these chains are further connected through O—H…O hydrogen bonds, leading to a three‐dimensional hydrogen‐bonded network. In polymer (II), each hexadentate L2? ligand coordinates to six CdII ions, resulting in a three‐dimensional network structure, in which all of the CdII ions and L2? ligands are equivalent, respectively. The IR spectra, thermogravimetric analyses and fluorescence properties of both reported compounds were investigated. |