Herein, we report on the synthesis, structural analysis, physicochemical characterization and photoluminescence performance of two ternary compounds based on dicarboxylate and bispyridyl-like ligands and metal ions of group 12, namely [Zn2(μ4-bdc)(μ-pbptz)(DMF)2(NO3)2]n (1-Zn) and {[Cd(μ3-bdc)(μ-pbptz)]·DMF}n (2-Cd) (where bdc = benzene-1,4-dicarboxylate, pbptz = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and DMF = N,N-dimethylformamide). 1-Zn, consisting of a 2D-layered framework, can be considered as the lower-dimensional analogue of the previously reported {[Zn2(μ4-bdc)2(μ-pbptz)]·2DMF·3H2O}n 3D MOF (1'-Zn), which is shown to recrystallize into 1-Zn undergoing a kind of exfoliation. 2-Cd presents a 3D doubly interpenetrated framework whose porosity is reduced to approximately half of the available solvent-accessible voids contained in the non-interpenetrated homologue reported so far, {[Cd(μ3-bdc)(μ-pbptz)]·3DMF}n (2'-Cd). Structural factors leading to each of the alternative frameworks are detailed by analysing the building units with a perusal of the Cambridge Structural Database and providing a comparative description of the structures. The photoluminescence properties of herein reported compounds (1-Zn and 2-Cd) are also measured and the processes governing the spectra are described using time-dependent density-functional theory (TD-DFT), which allows establishing some structural correspondences by comparing these results with those of the 1'-Zn and 2'-Cd analogues.