Insights into Nd III to Yb III Energy Transfer and Its Implications in Luminescence Thermometry.

Autor: Oggianu M; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy., Mameli V; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy., Hernández-Rodríguez MA; Phantom-g, Department of Physics, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal., Monni N; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy., Souto M; Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal., Brites CDS; Phantom-g, Department of Physics, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal., Cannas C; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy., Manna F; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy., Quochi F; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy.; Dipartimento di Fisica, Università degli Studi di Cagliari, Complesso Universitario di Monserrato, Monserrato I-09042, Italy., Cadoni E; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy., Masciocchi N; Dipartimento di Scienza e Alta Tecnologia & To.Sca.Lab., Università degli Studi dell, via Valleggio 11, Como 22100, Italy., Carneiro Neto AN; Phantom-g, Department of Physics, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal., Carlos LD; Phantom-g, Department of Physics, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal., Mercuri ML; Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.; INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy.
Jazyk: angličtina
Zdroj: Chemistry of materials : a publication of the American Chemical Society [Chem Mater] 2024 Mar 28; Vol. 36 (7), pp. 3452-3463. Date of Electronic Publication: 2024 Mar 28 (Print Publication: 2024).
DOI: 10.1021/acs.chemmater.4c00362
Abstrakt: This work challenges the conventional approach of using Nd III 4 F 3/2 lifetime changes for evaluating the experimental Nd III → Yb III energy transfer rate and efficiency. Using near-infrared (NIR) emitting Nd:Yb mixed-metal coordination polymers (CPs), synthesized via solvent-free thermal grinding, we demonstrate that the Nd III [ 2 H 11/2 → 4 I 15/2 ] → Yb III [ 2 F 7/2 → 2 F 5/2 ] pathway, previously overlooked, dominates energy transfer due to superior energy resonance and J -level selection rule compatibility. This finding upends the conventional focus on the Nd III [ 4 F 3/2 → 4 I 11/2 ] → Yb III [ 2 F 7/2 → 2 F 5/2 ] transition pathway. We characterized Nd 0.890 Yb 0.110 (BTC)(H 2 O) 6 as a promising cryogenic NIR thermometry system and employed our novel energy transfer understanding to perform simulations, yielding theoretical thermometric parameters and sensitivities for diverse Nd:Yb ratios. Strikingly, experimental thermometric data closely matched the theoretical predictions, validating our revised model. This novel perspective on Nd III → Yb III energy transfer holds general applicability for the Nd III /Yb III pair, unveiling an important spectroscopic feature with broad implications for energy transfer-driven materials design.
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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