On the way to copper(I) iodide coordination polymers with specific luminescent properties, the in situ reduction of Cu(II) in the presence of KI and Inderitate N = heteroatomic ligand, either pyrazine (pyz) or 4,4'-bipyricline (bpy), resulted in one two-dimensional and two three-diniensional new coordination networks. Starting from,Cu(NO3)(2). 3H(2)O in the presence of pyzy successive precipitation of known yelow [((CuI)-I-I)(2)(pyz)(n), new orange [((CuI)-I-I)(2)(pyz)(n), and new dark blue {[Cu-I(p-yz)(2)]center dot I-5}(n) polymeric solids was observed. Starting from the same salt in the presence of resulted in, The. successive precipitation of known yellow, [((CuI)-I-I)(2)(bpy)] and new brown {[Cu-ll(NO3)(bpy)(2)].I-3 (dnif center dot H2O)}(n) coordination polymers. By using either Cu(CH3 COO)(2).H2O or Cu(BF4)(2) as starting materials, both known forms, yellow and [((CuI)-I-I)(2) (bpy)](n) orange [(CuI)-I-I(bpy)](n), precipitated successively. The new solid's. were characterized by IR spectroscopy and X-ray analysis.[(CuI)-I-I(pyz)](n), -i represents the missing member in the'xow of two-dimensional coordination networks with general formula [(CuI)-I-I(bpy)](n), (X = CI, Br, I) Its steady State and time-resolved characterization together with DFT and TDDFT calculations -,revealed that the emission at room ternReinture is mainly delayed fluorescence originating from mixed singlet metal-to-ligancl charge transfer'anel halicieLto-ligand charge transfer states,while-that at 77 K is phosphorescence, associated with the small singlet-triplet energy differences (triangle E= 70 meV).