A substituent decorating strategy for modification of the functional cavity is of great importance in the design of metal−organic frameworks (MOFs). Herein, three new isostructural cationic MOFs, [Cu 3 (Xpip) 2 ]•NO 3 •nH 2 O (Xpip stands for Xsubstituted phenylimidazophenanthroline, where X = adm (SCNU-2), f (SCNU-3), and none for SCNU-4), have been successfully synthesized and shown gyroidal utc-c topology and large pore sizes which can be adjusted by different substituents (−N(CH 3 ) 2 , −F, and −H). Interestingly, the differences of the substituents (sizes and proton donor/acceptor) show essential effects on the adsorption abilities of carbon dioxide and dyes, where SCNU-4 exhibits the highest CO 2 affinity and the biggest adsorption capacity for anionic dyes Fluorescein Sodium, and SCNU-3 adsorbs the largest amount (1503.6 mg/g) of Acid Fuchsin to date for the reported porous materials. The detailed studies in adsorption kinetics, adsorption isotherms, and theoretical calculation of the binding energies between the structures and dye molecules confirm that the electric properties of the frameworks (cationic) and substituents directed to the pore surface are two important factors dramatically affecting the selective dye adsorption.

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