Di(2-thienyl)imide, 1, has been shown to chemically polymerize, and, if metal complexes of 1 could be synthesized, the polymer could have potential applications as an ion sensor and environmental remediation agent. As a first step towards this goal, di(2thienyl)imide is shown to form complexes with Mn (II), Co (II), and Zn (II) perchlorates. The complexes of Mn 2+ and Co 2+ are isostructural with two di(2-thienyl)imide ligands in equatorial positions and two perchlorate ions axial. The Zn 2+ complex has two water molecules in the axial positions and the thiophene rings in the two equatorial ligands are tilted in the same direction from the median plane due to intra-and intermolecular contacts. The crystal structures and infrared spectra, as well as an improved synthesis and polymerization of di(2-thienyl)imide, are reported and discussed.