Hofmann coordination polymers (CPs) with cationic ligands provide an innovative strategy for recognizing π-electron-rich aromatic molecules – similar to the “little blue box”. In this study, we demonstrate that hydroquinone molecules can be incorporated into these coordination polymers when redox-active bipyridinium derivatives are used as axial ligands. The insertion leads to a significant structural modification, resulting in a shift of the spin transition by 150 K and an approximate 23 % increase in volume, caused by the strong donor-acceptor π-π stacking interaction formed between the ligands and the guest molecule. These findings have been confirmed through temperature-dependent single crystal X-ray diffraction, magnetic measurements and optical reflectivity measurements.