1,2-Bis[(2,6-diisopropyl-4-diethylmalonophenyl)imino]acenaphthene (Dem-Bian) with zinc chloride forms complex [(Dem-Bian)ZnCl2] (I). The reaction of complex I with n-BuLi proceeds with the deprotonation of the malonate fragments and gives 1D coordination polymer [ZnCl2(Dem-Bian)Li(DME)2]n (II). The reaction of [(Dem-Bian)CuCl] with n-BuLi affords 1D polymer [(Dem-Bian)Li2(DME)2]n (III). Compounds I–III are characterized by elemental analysis and IR spectroscopy. Derivatives I and II are characterized by 1Н NMR spectroscopy. The crystal structures of compounds II and III are determined by X-ray diffraction (XRD). Their thermal stability is studied by thermogravimetric analysis.