Selective separation of light hydrocarbons (LHs) and adsorption of volatile organic compounds (VOCs) remain expensive and complex scientific challenges in the petrochemical industry. Shape-selective adsorbent materials can cost-effectively face these demands. Two new porous, dynamic and amorphous metal-organic frameworks (MOFs), NEU-3 [= Zn(PMDA)(Py)2] and NEU-4 [= Fe(PMDA)(Py)2] are disclosed. These MOFs along with NEU-1c [= Zn(BPDI)(Py)2] and NEU-2 [= Fe(BPDI)(Py)2] display an electron-deficient pore surface due to predesigned π-electron-deficient ligands. They are unique smart guest-responsive materials owing to their π Lewis acidic pore surface and presumably their framework flexibility. A variety of effective adsorptions and adsorptive separations is achieved by using beds of NEU-1c, NEU-2, NEU-3 and NEU-4. Promising for further investigations into the petrochemical industry, NEU-4 shows ultrahigh benzene adsorption, recognition capability, selectivity for benzene over its analogues, and high stability and regenerability.