Anion-Cation Mediated Structural Rearrangement of an In-derived Three-Dimensional Interpenetrated Metal-Organic...

Area of Science:

• Materials Science
• Chemistry
• Nanotechnology

Background:

• Postsynthetic modification is a key strategy for creating complex metal-organic frameworks (MOFs).
• Traditional solvothermal synthesis methods often face limitations in producing certain MOF architectures.
• Developing new synthetic routes is crucial for expanding the library of accessible MOF structures.

Purpose of the Study:

• To report a novel anion-cation assisted solid-state transformation of a 3D MOF (ATF-1) into 2D structures (YCM-21-Z).
• To demonstrate the synthesis of a chemically unique MOF, YCM-21-Bnpy, unattainable through conventional solvothermal methods.
• To elucidate the mechanism underlying this solid-state transformation process.

Main Methods:

• Solid-state transformation of a 3D MOF (ATF-1) using quaternary ammonium halides.
• Characterization of the resulting 2D MOF structures (YCM-21-Z).
• Mechanistic studies involving halide-mediated de-intercalation and cation-assisted structural changes.

Main Results:

• Successful conversion of ATF-1 to a series of 2D MOFs (YCM-21-Z) without external building blocks.
• Phase-pure synthesis of the unique framework YCM-21-Bnpy, which is not achievable via solvothermal routes.
• Identification of nucleophilic halide-mediated de-intercalation and In secondary building unit flattening as key mechanistic steps.

Conclusions:

• Anion-cation assisted solid-state transformation offers a powerful route for MOF diversification.
• This method enables the synthesis of novel MOF architectures with unique properties.
• Understanding the mechanism provides insights for designing future MOF synthesis strategies.