The reaction between Zn(NO3)(2)center dot 6H(2)O or Zn(CH3COO)(2)center dot 2H(2)O and isophthalic acid (1,3-H(2)bdc) in the presence of benzimidazole (Hbzim) in dimethylformamide (DMF)/ethanol (EtOH)/H2O solvent mixture at room temperature yielded two structurally different coordination polymers: [Zn-2(1,3-bdc)(2)(Hbzim)(2)] (1) and [Zn-2(1,3-bdc)(bzim)(2)] (2). (1) is a 2D-layered framework with a molecule of benzimidazole coordinated to the Zn center, whereas (2) is a 3D framework with benzimidazolate species acting as a co-ligand and bridging two Zn(II) ions. Reactions performed at 90 degrees C led to the formation of coordination polymers structurally similar to (2), independently of the Zn(II) source used. In the absence of benzimidazole, the reaction between ZnAc2.2H(2)O and 1,3-H(2)bdc at 90 degrees C resulted in the formation of (3), a 3D coordination polymer Zn(HCOO)(3)(Me2NH2+). It was observed that the thermostability and the photo-physical properties of (1) and (2) are strongly dependent on the coordination modes and packing of benzimidazole in the solid state. These materials present photoluminescence in the wide range of the spectrum, from UV to IR. A full understanding of a physical process occurring in these intriguing systems, including complete energy level diagrams with possible transitions were provided. (C) 2015 Elsevier B.V. All rights reserved.