Strongly blue fluorescent 1-phenyl-2-(pyridin-2-yl)-1H-phenanthro[9,10-d]imidazole (L1) is a facile block for the construction of multichromophore organic molecules, and simultaneously serves as a chelating diimine ligand. The coordination of L1 to zinc halides enhances the intraligand charge transfer and decreases the emission energy. For the iodide derivative, intra- and intermolecular heavy atom effects lead to a dual singlet–triplet emission with a temperature-dependent ratio of fluorescence and phosphorescence bands in the crystalline state. Decoration of the anthracene core with pyridyl-phenanthroimidazole units (L2 and L3) changes the localization of the lowest energy electronic transitions to the former polyaromatic motif. The solid-state photophysical characteristics of L2 and L3-based compounds strongly depend on the intermolecular interactions between the constituting π-systems (phenanthrene and anthracene), which are perturbed by the ZnX₂ coordinated fragments. Modulation of π-stacking contacts in these molecular materials containing L2 and L3 chromophores forms a basis for dynamic optical properties, responsive to mechanical, thermal, or chemical stimuli.