A series of d(10) dicyanometallate polymeric compounds were studied by electronic spectroscopy and density functional theory (DFT) calculations. In these materials, the negatively charged one-dimensional (1D) polymeric chains are linked together by [M(en)(2)](2+) (M = Cu(II) and Zn(II); en = ethylenediamine). More than innocent building blocks, the [M(en)2] units offer a possible synthetic way to modify electronic properties of the materials. Through its low energy d-d excited state, the d(9) copper(II) ions offer deactivation pathways for the normally emissive dicyanometallate polymer. Deactivation was shown to be specific to the excited state energy.