Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal-Organic Frameworks

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal-organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {Sr^IICu^II₆[(S,S)-methox]_1.5[(S,S)-Mecysmox]_1.50(OH)₂(H₂O)}·36H₂O (5), featuring narrow functional channels decorated with both -CH₂SCH₃ and -CH₂CH₂SCH₃ thioalkyl chains-from l-methionine and l-methylcysteine amino acid-derived ligands, respectively-stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions-less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.