4.7 Article

Unveiling the Structure-Modulator Relationships in Thorium-Based Metal-Organic Framework Crystallization

Journal

INORGANIC CHEMISTRY
Volume 62, Issue 14, Pages 5479-5486

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c04447

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This study investigates the structure-modulator relationship in the synthesis of thorium-based MOFs using different modulators and the ligand H4ATC. The results show that formic acid and acetic acid compete with H4ATC to form NU-52 and NU-54, while trifluoroacetic acid and benzoic acid result in NU-53 and NU-55. The identity and amount of modulator play a crucial role in determining the Th-based MOF structures with H4ATC as the coordinated ligand.
Acid modulator has been the most widely employed ingredient for highly crystalline metal-organic framework (MOF) synthesis. However, the mechanistic understanding of thorium (Th)based MOF crystallization remains a great challenge due to the intrinsic properties of fast olation and oxolation reactions of Th species in solution. Here, we constructed a series of Th-based MOFs by adding different modulators (formic acid, acetic acid, trifluoroacetic acid, and benzoic acid) to a synthetic solution along with tetratopic 1,3,5,7adamantane tetracarboxylic acid (H4ATC), a three-dimensional (3D) ligand with a rigid aliphatic backbone. This work presents an in-depth study of the structure-modulator relationship between the H4ATC ligand and coordinating modulators in the Th-based MOF crystallization process. Crystal structures of these Th-based MOFs reveal that formic acid and acetic acid modulators can compete with the H4ATC ligand to form NU-52 and NU-54; these MOFs possess Th nodes linked by the corresponding modulator. Alternatively, usage of trifluoroacetic acid and benzoic acid modulators results in NU 53 and NU-55; these MOFs possess Th nodes coordinated by only the H4ATC ligand, regardless of the modulator amount. This work highlights that both the identity and amount of modulator play a crucial role in determining the resulting Th-based MOF structures when H4ATC is selected as the coordinated ligand.

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