Lanthanide Contraction Associated Coordination Regimes and Photocatalytic Performance of Polyoxometalate-Based Lanthanide Phosphonates.

Authors

Lin-Lin Wang, Hong-Li Jia, Jian-Jie Xu, Qi-Ming Qiu, Chuan-Bing Hou, Wei Li, Hong-Liang Han, Heng-Yun Ye, Rui-Lin Yang, Qiong-Hua Jin

Published in

Inorganic chemistry. Volume 65. Issue 41. Pages 24319-24330. Oct 19, 2026.

Abstract

Lanthanide contraction provides a continuous scale for tuning coordination structures, yet its systematic use in photoactive materials remains underexplored. Herein, 14 POM-phosphonate-lanthanide hybrids from La to Lu (excluding Pm) were synthesized under mild conditions. Single-crystal XRD identifies three coordination regimes: La3+ at the eight/nine-coordination boundary, Ce3+-Yb3+ adopting stable eight-coordination, and Lu3+ undergoing a ligand-deficient transition due to steric congestion. The Sm3+ complex 5b, obtained under diffusion conditions, exhibits the same motif as Lu3+ complex, indicating that crystal growth conditions can influence coordination-mode selection. Combined with band-structure analysis, EIS, radical trapping, EPR, and HPLC-MS, the photocatalytic mechanism was investigated. This work converts lanthanide contraction from a descriptive concept into an experimental framework for constructing structure-performance correlations.

PMID:
42895379
Bibliographic data and abstract were imported from PubMed on 19 Oct 2026.

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