Solvent-Induced Structural Diversity of Partially Fluorinated, Stable Pb(II) Metal–Organic Frameworks and Their Luminescence Properties

Rigid, linear partially fluorinated ligand 2,2′-bis-trifluoromethyl-biphenyl-4,4′-dicarboxylic acid (<b>H</b>_<b>2</b><b>L</b>) was synthesized and used to construct five metal organic frameworks with Pb­(II) through hydro- and solvothermal techniques. Depending on the nature of the solvent or solvent mixture, five different coordination polymers, {[Pb₆(L)₅(OH)₂]·2H₂O}_<i>n</i> (<b>1</b>), {[Pb₃(L)₂(O)­(EtOH)]·(EtOH)}_<i>n</i> (<b>2</b>), {[Pb₃(L)₂(O)­(PrOH)]·(PrOH)}_<i>n</i> (<b>3</b>), {[Pb₃(L)₂(O)­(<i>i</i>-PrOH)]·(<i>i</i>-PrOH)}_<i>n</i> (<b>4</b>), and {[Pb₆(L)₄(O)₂]·(benzylalcohol)₂(H₂O)₂}_<i>n</i> (<b>5</b>), were synthesized. All of these compounds were characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, elemental analysis, and powder X-ray diffraction measurements. Complex <b>1</b>, which is a 3D MOF, can be synthesized hydrothermally. However, isostructural complexes <b>2</b>–<b>4</b> can be obtained solvothermally using ethanol, propanol, and isopropanol, respectively, with water. The alcohols (ethanol, propanol, and isopropanol) are incorporated in the final 3D structures. Complex <b>5</b>, having a 2D layer structure, was synthesized using a benzyl alcohol and water mixture. All of the complexes exhibit rare rod-type topology. Solid-state photoluminescence studies were carried out for all of the complexes at room temperature

Solvent-Induced Structural Diversity of Partially Fluorinated, Stable Pb(II) Metal–Organic Frameworks and Their Luminescence Properties

Rigid, linear partially fluorinated ligand 2,2′-bis-trifluoromethyl-biphenyl-4,4′-dicarboxylic acid (<b>H</b>_<b>2</b><b>L</b>) was synthesized and used to construct five metal organic frameworks with Pb­(II) through hydro- and solvothermal techniques. Depending on the nature of the solvent or solvent mixture, five different coordination polymers, {[Pb₆(L)₅(OH)₂]·2H₂O}_<i>n</i> (<b>1</b>), {[Pb₃(L)₂(O)­(EtOH)]·(EtOH)}_<i>n</i> (<b>2</b>), {[Pb₃(L)₂(O)­(PrOH)]·(PrOH)}_<i>n</i> (<b>3</b>), {[Pb₃(L)₂(O)­(<i>i</i>-PrOH)]·(<i>i</i>-PrOH)}_<i>n</i> (<b>4</b>), and {[Pb₆(L)₄(O)₂]·(benzylalcohol)₂(H₂O)₂}_<i>n</i> (<b>5</b>), were synthesized. All of these compounds were characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, elemental analysis, and powder X-ray diffraction measurements. Complex <b>1</b>, which is a 3D MOF, can be synthesized hydrothermally. However, isostructural complexes <b>2</b>–<b>4</b> can be obtained solvothermally using ethanol, propanol, and isopropanol, respectively, with water. The alcohols (ethanol, propanol, and isopropanol) are incorporated in the final 3D structures. Complex <b>5</b>, having a 2D layer structure, was synthesized using a benzyl alcohol and water mixture. All of the complexes exhibit rare rod-type topology. Solid-state photoluminescence studies were carried out for all of the complexes at room temperature

Gas Storage in a Partially Fluorinated Highly Stable Three-Dimensional Porous Metal–Organic Framework

A partially fluorinated linear rigid linker, 2,2′-bis-trifluoromethyl-biphenyl-4,4′-dicarboxylic acid (H₂bfbpdc), has been synthesized. This linker forms a porous three-dimensional (3D) metal–organic framework, {[Zn₄O­(bfbpdc)₃(bpy)_0.5(H₂O)]·(3DMF)­(H₂O)}_<i>n</i> (<b>1</b>), in the presence of the colinker 4,4′-bipyridine (bpy) and Zn­(NO₃)₂·6H₂O under solvothermal condition. Single crystal X-ray analysis shows that <b>1</b> contains a 3D channel structure with highly polar pore surfaces decorated with pendant trifluoromethyl groups of bfbpdc^2– linker. Thermogravimetric analysis (TGA) and variable temperature powder X-ray diffraction (VTPXRD) exhibit high thermal stability of the framework. The solvent molecules present in the voids can be removed by heating, maintaining the integrity of the structure to afford a porous framework. Gas (N₂, H₂, CH₄, and CO₂) and water adsorption studies were performed on this framework