Metal-Organic Frameworks as Unique Platforms to Gain Insight of σ-Hole Interactions for the Removal of Organic Dyes from Aquatic Ecosystems
2022
Negro, Cristina | Escamilla, Paula | Bruno, Rosaria | Ferrando Soria, Jesús | Armentano, Donatella | Pardo Marín, Emilio
The combination of high crystallinity and rich host-guest chemistry in metal-organic frameworks (MOFs), have situated them in an advantageous position, with respect to traditional porous materials, to gain insight on specific weak noncovalent supramolecular interactions. In particular, sulfur σ-hole interactions are known to play a key role in the biological activity of living beings as well as on relevant molecular recognitions processes. However, so far, they have been barely explored. Here, we describe both how the combination of the intrinsic features of MOFs, especially the possibility of using single-crystal X-ray crystallography (SCXRD), can be an extremely valuable tool to gain insight on sulfur σ-hole interactions, and how their rational exploitation can be enormously useful in the efficient removal of harmful organic molecules from aquatic ecosystems. Thus, we have used a MOF, prepared from the amino acid L-methionine and possessing channels decorated with −CH2CH2SCH3 thioalkyl chains, to remove a family of organic dyes at very low concentrations (10 ppm) from water. This MOF is able to efficiently capture the four dyes in a very fast manner, reaching within five minutes nearly the maximum removal. Remarkably, the crystal structure of the different organic dyes within MOFs channels could be determined by SCXRD. This has enabled us to directly visualize the important role sulfur σ-hole interactions play on the removal of organic dyes from aqueous solutions, representing one of the first studies on the rational exploitation of σ-hole interactions for water remediation.
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