This article describes a unique synthetic route that enables a neutral mono(dithiolene)metal unit, {Zn(dmit)}, to link with three different organic molecules, resulting in the isolation of a new class of neutral coordination polymers. The species {Zn(dmit)} coordinates with 4,4′-bipyridine (4,4′-bpy), trans-1,2-bis(4-pyridyl)ethene (4,4′-bpe) and 1,4-bis(imidazole-1-ylmethyl)-benzene (bix) as linkers giving rise to the formation of coordination polymers [Zn(dmit)(4,4′-bpy)]_n (1), [Zn(dmit)(4,4′-bpe)]_n (2) and [Zn(dmit)(bix)]_n (3) respectively. Compounds 1–3 were characterized by elemental analyses, IR, diffuse reflectance and single crystal X-ray diffraction studies. Compounds 1 and 3 crystallize in the monoclinic space groupP2₁/n, whereby compound 2 crystallizes in triclinic space group P. In the present study, we chose three linkers 4,4′-bpy, 4,4′-bpe and bix (see Schemes 1–3, respectively, for their structural drawings), that differ in terms of their molecular dimensions. The crystal structures of compounds 1–3 are described here in terms of their supramolecular diversities that include π–π interactions, not only among aromatic stacking (compounds 1 and 3), but also between an aromatic ring and an ethylenic double bond (compound 2). The electronic absorption spectroscopy of compounds 1–3 support these intermolecular π–π interactions.