A 2D cyanido-bridged architecture ZnII-[WV(CN)8]3– is smoothly pillared by N,N'-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPNDI) into 3D hybrid porous coordination polymer (PCP) . It shows significant uptake of H2O, MeOH or CHCl3 vapours with easy regeneration to the native form, and breathing-type CO2 adsorption contrasting non-porosity towards N2, providing a new example of highly flexible porous material.

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