Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal-Organic Frameworks through a...

Area of Science:

• Materials Science
• Crystallography
• Chemistry

Background:

• Reticular chemistry enables diverse metal-organic frameworks (MOFs).
• Frameworks from discrete secondary building units (SBUs) dominate.
• Synthesis of MOFs with infinite rod-shaped SBUs is underdeveloped.

Purpose of the Study:

• To design and synthesize novel MOFs using infinite rod-shaped SBUs.
• To explore linker desymmetrization as a strategy for MOF construction.
• To investigate the adsorption properties of the novel MOF.

Main Methods:

• Global linker desymmetrization approach.
• Micro electron diffraction (MicroED) crystallography for structure determination.
• Multicycle breakthrough experiments for adsorption studies.
• Density functional theory (DFT) calculations.

Main Results:

• A novel copper MOF (Cu-ASY) with infinite Cu-carboxylate rod SBUs was synthesized.
• The structure features a unique 3,5-connected gfc net composed of [4^3.6^2] tiles.
• Cu-ASY exhibits permanent ultramicroporosity with 1D channels and inert surfaces.
• Selective adsorption of propane (C3H8) over propene (C3H6) was achieved with high efficiency.
• Propane adsorption is driven by van der Waals interactions with the MOF surface.

Conclusions:

• Linker desymmetrization is an effective strategy for creating unique MOF structures.
• Cu-ASY demonstrates potential for selective gas separation applications.
• The study provides insights into structure-property relationships in MOFs.