Luminescent Ln 3+ -based silsesquioxanes with a β-diketonate antenna ligand: toward the design of efficient temperature sensors.

Autor: Félix G; CNRS, ENSCM, University Montpellier, Montpellier, France., Kulakova AN; CNRS, ENSCM, University Montpellier, Montpellier, France.; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia., Sene S; CNRS, ENSCM, University Montpellier, Montpellier, France., Khrustalev VN; Peoples' Friendship University of Russia (RUDN University), Moscow, Russia.; Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia., Hernández-Rodríguez MA; Phantom-g, Physics Department and CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro, Portugal.; Departamento de Física, Universidad de La Laguna San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain., Shubina ES; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia., Pelluau T; CNRS, ENSCM, University Montpellier, Montpellier, France., Carlos LD; Phantom-g, Physics Department and CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro, Portugal., Guari Y; CNRS, ENSCM, University Montpellier, Montpellier, France., Carneiro Neto AN; Phantom-g, Physics Department and CICECO-Aveiro Institute of Materials, University of Aveiro, Aveiro, Portugal., Bilyachenko AN; Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia.; Peoples' Friendship University of Russia (RUDN University), Moscow, Russia., Larionova J; CNRS, ENSCM, University Montpellier, Montpellier, France.
Jazyk: angličtina
Zdroj: Frontiers in chemistry [Front Chem] 2024 Apr 03; Vol. 12, pp. 1379587. Date of Electronic Publication: 2024 Apr 03 (Print Publication: 2024).
DOI: 10.3389/fchem.2024.1379587
Abstrakt: We report the synthesis and single-crystal X-ray diffraction, magnetic, and luminescence measurements of a novel family of luminescent cage-like tetranuclear silsesquioxanes (PhSiO 1.5 ) 8 (LnO 1.5 ) 4 (O)(C 5 H 8 O 2 ) 6 (EtOH) 2 (CH 3 CN) 2 ⋅2CH 3 CN (where Ln = Tb, 1 ; Tb/Eu, 2 ; and Gd, 3 ), featuring seven-coordinated lanthanide ions arranged in a one-capped trigonal prism geometry. Compounds 1 and 2 exhibit characteristic Tb 3+ and Tb 3+ /Eu 3+ -related emissions, respectively, sensitized by the chelating antenna acetylacetonate (acac) ligands upon excitation in the UV and visible spectral regions. Compound 3 is used to assess the energies of the triplet states of the acac ligand. For compound 1 , theoretical calculations on the intramolecular energy transfer and multiphonon rates indicate a thermal balance between the 5 D 4 Stark components, while the mixed Tb 3+ /Eu 3+ analog 2 , with a Tb:Eu ratio of 3:1, showcases intra-cluster Tb 3+ -to-Eu 3+ energy transfer, calculated theoretically as a function of temperature. By utilizing the intensity ratio between the 5 D 4 → 7 F 5 (Tb 3+ ) and 5 D 0 → 7 F 2 (Eu 3+ ) transitions in the range 11-373 K, we demonstrate the realization of a ratiometric luminescent thermometer with compound 2 , operating in the range 11-373 K with a maximum relative sensitivity of 2.0% K -1 at 373 K. These findings highlight the potential of cage-like silsesquioxanes as versatile materials for optical sensing-enabled applications.
Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision.
(Copyright © 2024 Félix, Kulakova, Sene, Khrustalev, Hernández-Rodríguez, Shubina, Pelluau, Carlos, Guari, Carneiro Neto, Bilyachenko and Larionova.)
Databáze: MEDLINE
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