resumo
This work challenges the conventional approach of using (NdF3/2)-F-III 4 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 [H-2(11/2) -> I-4(15/2)] -> Yb-III [F-2(7/2) -> F-2(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 [F-4(3/2) -> I-4(11/2)] -> Yb-III [F-2(7/2) -> F-2(5/2)] 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 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.
palavras-chave
METAL-ORGANIC FRAMEWORKS; COORDINATION POLYMERS; FLUORESCENCE; TRANSITIONS; COMPLEXES; SPECTRA; IONS; NANOTHERMOMETERS; INTENSITIES; LANTHANIDES
categoria
Chemistry; Materials Science
autores
Oggianu, M; Mameli, V; Hernández-Rodríguez, MA; Monni, N; Souto, M; Brites, CDS; Cannas, C; Manna, F; Quochi, F; Cadoni, E; Masciocchi, N; Neto, ANC; Carlos, LD; Mercuri, ML
nossos autores
Albano Neto Carneiro Neto
Investigador Júnior
Carlos Brites
Professor associado
Luís Carlos
Professor Catedrático
Manuel Souto Salom
Professor Auxiliar Convidado
Miguel Andrés Hernández Rodríguez
Investigador JúniorGrupos
G2 - Materiais Fotónicos, Eletrónicos e Magnéticos
G3 - Materiais Eletroquímicos, Interfaces e Revestimentos
Projectos
Redox-active Metal-Organic Frameworks as Electrode Materials for Lithium-Ion Batteries (RedoxMOFs)
agradecimentos
Fondazione di Sardegna-Convenzione triennale tra la Fondazione di Sardegnae gli Atenei Sardi, Regione Sardegna-L.R. 7/2007 annualita2020, through Project 'Smart supramolecular Materials for Anionsensing and Water Remediation (SMAWRT),' CUP: F75F21001260007,is acknowledged for financial support. FCT/MCTES-The Shape of Water (PTDC/NAN-PRO/3881/2020), LogicALL (PTDC/CTM-CTM/0340/2021) and RedoxMOFs (PTDC/QUI-ELT/2593/2021) financed by Portuguese funds.