Dataset Information

Eu³⁺ and Tb³⁺ @ PSQ: Dual Luminescent Polyhedral Oligomeric Polysilsesquioxanes.

ABSTRACT: The synthesis and characterization of novel luminescent amorphous POSS-based polysilsesquioxanes (PSQs) with Tb³⁺ and Eu³⁺ ions directly integrated in the polysilsesquioxane matrix is presented. Two different Tb³⁺/Eu³⁺ molar ratios were applied, with the aim of disclosing the relationships between the nature and loading of the ions and the luminescence properties. Particular attention was given to the investigation of site geometry and hydration state of the metal centers in the inorganic framework, and of the effect of the Tb³⁺ → Eu³⁺ energy transfer on the overall optical properties of the co-doped materials. The obtained materials were characterized by high photostability and colors of the emitted light ranging from orange to deep red, as a function of both the Tb³⁺/Eu³⁺ molar ratio and the chosen excitation wavelength. A good energy transfer was observed, with higher efficiency displayed when donor/sensitizer concentration was lower than the acceptor/activator concentration. The easiness of preparation and the possibility to finely tune the photoluminescence properties make these materials valid candidates for several applications, including bioimaging, sensors, ratiometric luminescence-based thermometers, and optical components in inorganic or hybrid light-emitting devices.

SUBMITTER: Marchesi S

PROVIDER: S-EPMC9694933 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Publications

Eu3+ and Tb3+ @ PSQ: Dual Luminescent Polyhedral Oligomeric Polysilsesquioxanes.

Marchesi Stefano S Miletto Ivana I Bisio Chiara C Gianotti Enrica E Marchese Leonardo L Carniato Fabio F

Materials (Basel, Switzerland) 20221112 22

The synthesis and characterization of novel luminescent amorphous POSS-based polysilsesquioxanes (PSQs) with Tb3+ and Eu3+ ions directly integrated in the polysilsesquioxane matrix is presented. Two different Tb3+/Eu3+ molar ratios were applied, with the aim of disclosing the relationships between the nature and loading of the ions and the luminescence properties. Particular attention was given to the investigation of site geometry and hydration state ...[more]

PMID: 36431482

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Project description:A family of homodinuclear Ln3+ (Ln3+ = Gd3+, Eu3+) luminescent complexes with the general formula [Ln2(β-diketonato)6(N-oxide)y] has been developed to study the effect of the β-diketonato and N-oxide ligands on their thermometric properties. The investigated complexes are [Ln2(tta)6(pyrzMO)2] (Ln = Eu (1·C7H8), Gd (5)), [Ln2(dbm)6(pyrzMO)2] (Ln = Eu (2), Gd (6)), [Ln2(bta)6(pyrzMO)2] (Ln = Eu (3), Gd (7)), [Ln2(hfac)6(pyrzMO)3] (Ln = Eu (4), Gd (8)) (pyrzMO = pyrazine N-oxide, Htta = thenoyltrifluoroacetone, Hdbm = dibenzoylmethane, Hbta = benzoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone, C7H8 = toluene), and their 4,4'-bipyridine N-oxide (bipyMO) analogues. Europium complexes emit a bright red light under UV radiation at room temperature, whose intensity displays a strong temperature (T) dependence between 223 and 373 K. This remarkable variation is exploited to develop a series of luminescent thermometers by using the integrated intensity of the 5D0 → 7F2 europium transition as the thermometric parameter (Δ). The effect of different β-diketonato and N-oxide ligands is investigated with particular regard to the shape of thermometer calibration (Δ vs T) and relative thermal sensitivity curves: i.e.. the change in Δ per degree of temperature variation usually indicated as Sr (% K-1). The thermometric properties are determined by the presence of two nonradiative deactivation channels, back energy transfer (BEnT) from Eu3+ to the ligand triplet levels and ligand to metal charge transfer (LMCT). In the complexes bearing tta and dbm ligands, whose triplet energy is ca. 20000 cm-1, both deactivation channels are active in the same temperature range, and both contribute to determine the thermometric properties. Conversely, with bta and hfac ligands the response of the europium luminescence to temperature variation is ruled by LMCT channels since the high triplet energy (>21400 cm-1) makes BEnT ineffective in the investigated temperature range.

Dataset Information

Eu³⁺ and Tb³⁺ @ PSQ: Dual Luminescent Polyhedral Oligomeric Polysilsesquioxanes.

Publications

Eu<sup>3+</sup> and Tb<sup>3+</sup> @ PSQ: Dual Luminescent Polyhedral Oligomeric Polysilsesquioxanes.

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