Authors
Tingting Li, Yaoqin Wu, Feng Jiang, HaiFeng Zhu, Shengrong He, Jiyu Sui, Cong Zhang, Zhennan Wu, Xue Bai
Published in
Nanoscale. Volume 18. Issue 24. Pages 12968-12975. Jun 25, 2026. Epub Jun 25, 2026.
Abstract
The optical properties of trivalent lanthanide ions (Ln3+) are restricted by their lattice sites, and there are still challenges in regulating their lattice sites and coordination environment at the atomic scale. This work proposes and validates a strategy of ligand engineering unit site regulation that achieves effective regulation of local coordination symmetry by precisely replacing a single coordination molecule on an atomically precise Eu4Ti9 cluster. We synthesized an Eu4Ti9 cluster protected by 4-trifluoromethyl benzoic acid (4-TFMBA), in which Eu3+ exists in two coordination configurations (Eu1 adopts a D4d arrangement, while Eu2 changes from D4d in Eu4Ti9-H to D2d in Eu4Ti9-P). Without changing the coordination environment of the Eu1 site, replacing the terminal water molecule ligand at the Eu2 site with triphenylphosphine oxide (TPPO) can significantly reduce the local symmetry and increases the photoluminescence quantum yield of the cluster from 11.32% to 28.94%. By combining crystallographic analysis, the Judd-Ofelt theory, and temperature-dependent spectroscopy, we clarify the quantitative structure-activity relationship between the local symmetry change, crystal field parameter evolution, and luminescence enhancement. This work not only reports creation of a class of luminescent clusters but also, more importantly, provides a new way to control the luminescence dynamics of lanthanide materials at atomic precision through rational ligand design, which is of great significance to the development of lanthanide-based materials.
PMID:
42348204
Bibliographic data and abstract were imported from PubMed on 25 Jun 2026.
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