Insights into NdIII to YbIII Energy Transfer and Its Implications in Luminescence Thermometry

Oggianu, Mariangela;Mameli, Valentina;Hernández-Rodríguez, Miguel A.;Monni, Noemi;Souto, Manuel;Brites, Carlos D. S.;Cannas, Carla;Manna, Fabio;Quochi, Francesco;Cadoni, Enzo;Masciocchi, Norberto;Carneiro Neto, Albano N.;Carlos, Luís D.;Mercuri, Maria Laura

Ultimo

2024-01-01

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Abstract

This work challenges the conventional approach of using NdIII 4F3/2 lifetime changes for evaluating the experimental NdIII → YbIII 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 NdIII [2H11/2 → 4I15/2] → YbIII [2F7/2 → 2F5/2] 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 NdIII [4F3/2 → 4I11/2] → YbIII [2F7/2 → 2F5/2] transition pathway. We characterized Nd0.890Yb0.110(BTC)(H2O)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 NdIII → YbIII energy transfer holds general applicability for the NdIII/YbIII pair, unveiling an important spectroscopic feature with broad implications for energy transfer-driven materials design.