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

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

doi:10.1021/acs.chemmater.4c00362

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

Chem Mater. 2024 Mar 28;36(7):3452-3463. doi: 10.1021/acs.chemmater.4c00362. eCollection 2024 Apr 9.

Authors

Mariangela Oggianu^{1

2}, Valentina Mameli^{1

2}, Miguel A Hernández-Rodríguez³, Noemi Monni^{1

2}, Manuel Souto⁴, Carlos D S Brites³, Carla Cannas^{1

2}, Fabio Manna¹, Francesco Quochi^{2

5}, Enzo Cadoni¹, Norberto Masciocchi⁶, Albano N Carneiro Neto³, Luís D Carlos³, Maria Laura Mercuri^{1

2}

Affiliations

¹ Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Monserrato I-09042, Italy.
² INSTM, Via Giuseppe Giusti, 9, Firenze 50121, Italy.
³ Phantom-g, Department of Physics, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal.
⁴ Department of Chemistry, CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro 3810-193, Portugal.
⁵ Dipartimento di Fisica, Università degli Studi di Cagliari, Complesso Universitario di Monserrato, Monserrato I-09042, Italy.
⁶ Dipartimento di Scienza e Alta Tecnologia & To.Sca.Lab., Università degli Studi dell, via Valleggio 11, Como 22100, Italy.

Abstract

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 [²H_11/2 → ⁴I_15/2] → Yb^III [²F_7/2 → ²F_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 [⁴F_3/2 → ⁴I_11/2] → Yb^III [²F_7/2 → ²F_5/2] transition pathway. We characterized Nd_0.890Yb_0.110(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 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.