Cooperativity and Anticooperativity Effects in a Cadmium-Based Metal-Organic Framework: Structural Characterization,...

Area of Science:

• Coordination Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Metal-organic frameworks (MOFs) offer tunable structures for diverse applications.
• Cadmium(II)-based MOFs are explored for their unique coordination properties.
• Understanding noncovalent interactions is crucial for designing stable MOF architectures.

Purpose of the Study:

• Synthesize and structurally characterize two new cadmium(II)-based MOF complexes.
• Investigate the supramolecular assembly and noncovalent interactions within the MOFs.
• Evaluate the catalytic performance of the synthesized MOFs in the Knoevenagel condensation reaction.

Main Methods:

• Single crystal X-ray diffraction for structural determination.
• Elemental analysis and thermogravimetric analysis for compositional and thermal stability.
• Density functional theory (DFT) studies, including NCI analysis, for computational insights.

Main Results:

• Two polynuclear cadmium(II)-MOFs, [CdL¹bpy]_n·nH₂L¹ (1) and [CdL²ClH₂O]_n (2), were successfully synthesized.
• Complex 1 forms a 3D polymeric network, while Complex 2 forms a 2D network, stabilized by hydrogen bonding and other noncovalent interactions.
• Complex 1 demonstrated high catalytic efficacy and recyclability for the Knoevenagel condensation at room temperature.

Conclusions:

• The synthesized cadmium(II)-MOFs exhibit distinct dimensionality and supramolecular architectures.
• DFT analysis elucidated the role of noncovalent interactions in stabilizing the 3D framework of Complex 1.
• Complex 1 shows promising potential as a recyclable heterogeneous catalyst for organic transformations.