1. Ag+-induced energy level splitting in Ln-MOFs achieves enhanced Eu3+ emission intensity.
- Author
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Zhai, Xiaoyong, Mu, Xijiao, Tan, Guoying, Liang, Lijuan, Kou, Yao, Su, Pingru, Yan, Chun-Hua, and Tang, Yu
- Abstract
In lanthanide (Ln) complexes, the oversight of f-electrons and inner-shell relativistic interactions has constituted a critical gap, limiting a nuanced understanding and modulation of their luminescent properties. Addressing this issue, our study introduces a pioneering series of Ln-based metal-organic frameworks (Ln-MOFs), designated as Ln-TCPP, utilizing tetraphenylpyrazine-derived ligand and Ln
3+ ions (Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) to modulate luminescence through advanced synthesis and theoretical analysis. We particularly emphasize the enhancement of Eu3+ luminescence in Ln-TCPP, where incorporating Ag+ ions to replace [(CH3 )2 NH2 ]+ within the Ln-MOFs plays a pivotal role. Theoretically, by employing time-dependent density functional theory (TD-DFT) with full-electron relativistic effects, we demonstrate that Ag+ ions induce a splitting in the energy levels of Eu3+ . This splitting effectively reduces the rate of non-radiative transitions, significantly amplifying Eu3+ emission intensity. Our findings not only fill a long-standing void in understanding the all-electron relativistic interaction between f-electrons in Ln-MOFs luminescence but also establish a new strategy for controlling and optimizing the luminescent efficacy of these materials for potential applications. [ABSTRACT FROM AUTHOR]- Published
- 2025
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