A Partially Fluorinated Three‐fold Interpenetrated Stable Metal‐Organic Framework with Selective CO 2 Uptake

The hydrothermal reaction of Zn(NO 3 ) 2 · H 2 O and a linear 2, 2′‐bis‐trifluoromethyl‐biphenyl‐4, 4′‐dicarboxylic acid ( H 2 L ) ligand with –CF 3 groups at each phenyl moiety of the biphenyl rings leads to the formation of a three‐fold interpenetrated metal‐organic framework (MOF), {[Zn 2.66 O 0.66 ( L ) 2 ] · 2H 2 O} n ( 1 ) at 180 °C. Single‐crystal X‐ray diffraction studies revealed that 1 is constructed from polynuclear clusters [Zn 4 O(COO) 6 ] as secondary building units (SBU). These SBU are connected through the L 2– to generate an overall three‐dimensional structure with a 6‐connected primitive cuboidal (α‐Po) network. Thermogravimetric analyses and variable temperature powder X‐ray diffraction measurements suggested that 1 is thermally stable. The porosity of 1 was estimated by N 2 , CO 2 , H 2 , and CH 4 at different temperatures. The framework showed high selectivity of CO 2 uptake over N 2 and CH 4 . Furthermore, solid‐state photoluminescence studies were carried out for complex 1 upon excitation at 275 nm at room temperature.