The molecular complexes K-4[Zr(DBQ)](4) and K-4[Zr(CA)(4)], where DBQ(2-) and CA(2-) stand respectively for deprotonated dihydroxybenzoquinone and chloranilic acid, are reported. The anionic metal complexes consist of Zr(IV) surrounded by four O,O-chelating ligands. Besides the preparation and crystal structures for the two complexes, we show that in the solid state the DBQ complex forms a 3-D open framework (with 22% accessible volume) that undergoes a crystal-to-crystal phase transition to a compact structure upon guest molecule release. This process is reversible. In the presence of H2O, CO2, and other small molecules, the framework opens and accommodates guest molecules. CO2 adsorption isotherms show that the framework breathing occurs only when a slight gas pressure is applied. Crystal structures for both the hydrated and guest free phases of K-4[Zr(DBQ)(4)] have been investigated.