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Abstract: A novel polymeric complex NaCo(o-pba)3(H2O)3 (o-Hpba=2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)benzonic acid) based on racemic N-arylphthalimidine ligand has been prepared and characterized by elemental analysis, spectroscopic and X-ray crystallography methods. In the compound, each Co(II) cation is coordinated by six O atoms from three carboxyl groups of o-pba− and three water molecules in fac-MA3B3 model forming a chiral tripodal Co(o-pba)3(H2O)3 − anion-complex, enantiomeric pairs of which are alternately arranged in head-to-head and tail-to-tail orientations giving rise to a meso-one-dimensional chain-like structure. The compound exhibits high stability and unusual triple-peak luminescence in DMSO solution at room temperature. [Copyright &y& Elsevier]