O,N,O-tridentate chelation directs Mn(II)/periodate activation toward Mn(V)=O formation and selective micropollutant oxidation.

Authors

Wenqiang Jia, Bin Fang, Jianyu Han, Zonghao Liu, Zeqi Chen, Di Tang, Chengye Song, Xian Cao, Chaoqun Tan, He Guo, Min Song

Published in

Journal of hazardous materials. Volume 518. Pages 143965. Oct 22, 2026. Epub Oct 22, 2026.

Abstract

Ligand coordination has emerged as an effective strategy for steering Mn(II)-mediated periodate (PI) activation toward the formation of high-valent manganese-oxo species for micropollutant degradation, yet the influence of N/O donor-site arrangement on catalytic reactivity remains poorly understood. Herein, the relationship between N/O donor-site arrangement and Mn(II)/PI reactivity toward organic pollutants was elucidated using structurally distinct ligands. Among the tested ligands, 2,6-pyridinedicarboxylic acid with an ortho-flanked pincer-like O,N,O-tridentate coordination motif exhibited the highest catalytic performance, outperforming ligands with alternative N/O donor-site configurations by 1.2-11.3-fold. This reactivity trend indicated a close association between N/O donor-site arrangement and catalytic performance within the examined ligand series. Mn(V)=O was suggested as a plausible high-valent Mn-oxo species involved in the nonradical oxidation pathway. Density functional theory calculations provided electronic-structure and thermodynamic support for the role of O,N,O chelation in modulating the electronic structure of the Mn center, promoting I-O bond polarization in the precursor complex, and favoring the proposed formation of Mn(V)=O. An ortho-chelation score was further proposed as an empirical descriptor of position-dependent reactivity within the examined ligand series. These results highlight the favorable association of the ortho-flanked O,N,O coordination motif with Mn(II)/PI activation and provide insight into ligand-assisted selective oxidation systems for water treatment.

PMID:
42913264
Bibliographic data and abstract were imported from PubMed on 24 Oct 2026.

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