Linker Enantiomericity Engineering in Reticular Frameworks for Architecting Robust Materials with Synergetic Open...

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Crystallography

Background:

• Chiral linkers influence reticular framework properties like pore size and topology.
• Previous studies show enantiopure vs. racemic linkers can yield different structures, but examples are rare and often serendipitous.

Purpose of the Study:

• To rationally design reticular materials using chiral linkers and Wallach's rule.
• To investigate the impact of linker enantiopurity on framework structure and function.
• To develop a new methodology for architecting functional reticular materials.

Main Methods:

• Metal-directed coordination assembly using enantiopure and racemic chiral linkers with Cu ions.
• Crystallization in water at room temperature.
• Gas sorption and breakthrough experiments for SF6/N2 separation.
• Theoretical simulations.

Main Results:

• Enantiopure linker yielded a homochiral, 3D porous framework (S-TAMOF-3D) with (10,3)-a srs topology.
• Racemic linker exclusively formed a 2D dense, non-porous layered structure (race-TAMOF-2D).
• Activated S-TAMOF-3D demonstrated efficient SF6/N2 separation due to triangle-shaped cavities and open Cu2+ sites.

Conclusions:

• Linker enantiopicity significantly expands structural diversity in reticular materials beyond traditional methods.
• Wallach's rule can guide the rational design of extended reticular materials with specific properties.
• This work presents a novel strategy for creating advanced functional reticular materials.