Coordination polymers (CPs) are an attractive area of research in coordination chemistry and crystal engineering due to their intriguing topological architectures and various applications. Schiff bases derived from 2,6-diacetylpyridine are suitable candidates for the development of magnetic homo- and/or heterometallic CPs. Herein, we present our method for the synthesis of Zn(II) and Cd(II) CPs based on the 2,6-diacetylpyridine bis(nicotinoylhydrazone) Schiff base ligand (H2L), which led to the obtention of two homo- {[ZnL]∙0.5dmf∙1.5H2O}n (1) and {[CdL]∙0.5dmf∙H2O}n (2) and as well as one heterometallic {[Zn0.75Cd1.25L2]∙dmf∙0.5H2O}n (3) 2D isostructural and isomorphous coordination layers, where dmf = N,N-dimethylformamide. The Monte Carlo generator of Special Quasirandom Structures code was used to generate the Special Quasirandom Structure (SQS) to find the sequence of metals in the CP 3 in a ratio of 0.75:1.25. All obtaining CPs accommodate solvent guest (water and dmf) molecules in their cage-shaped interlayer spaces, which are released when the samples are heated. Thus, the association of thermal and IR methods was used to degas the accommodated guest samples at different temperatures (140 and 240/250°C) and their photoluminescent (PL) and adsorption-desorption properties were recorded in order to validate this assumption. The degassing crystals reveal a significant increase of volume pores and specific surface area, as well as PL emission with respect to synthesized ones (Figure 1). These findings make the layered compounds excellent small solvent sensor materials, expanding the family of CPs with interesting properties. Figure 1. Schematic representation of the synthesis of coordination compounds 1–3, photos of synthesized and degassed crystals and comparable solid-state emission plots (λex = 337 nm) for compounds 1–3 and degassed samples.