Upconversion Effective Enhancement by Producing Various Coordination Surroundings of Rare-Earth Ions

In this manuscript, we present a simple route to enhance upconversion (UC) emission by producing two different coordination sites of trivalent cations in a matrix material and adjusting crystal field asymmetry by Hf⁴⁺ co-doping. A cubic phase, Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂, with these structural characteristics was synthesized successfully by introducing a small ion (Al³⁺) into YF₃. X-ray diffraction (XRD), nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), X-ray spectroscopy (XPS), and fluorescence spectrophotometry (FS) were employed for its crystalline structure and luminescent property analysis. As a result, the coordination environments of the rare-earth ions were varied more obviously than a hexagonal NaYF₄ matrix with the same Hf⁴⁺ co-doping concentration, with vertical comparison, UC luminescent intensities of cubic Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂ were largely enhanced (∼32–80 times greater than that of different band emissions), while the maximum enhancement of hexagonal NaYF₄ was by a factor of ∼12. According to our experimental results, the mechanism has been demonstrated involving the crystalline structure, crystal field asymmetry, luminescence lifetime, hypersensitive transition, and so on. The study may be helpful for the design and fabrication of high-performance UC materials

Upconversion Effective Enhancement by Producing Various Coordination Surroundings of Rare-Earth Ions

In this manuscript, we present a simple route to enhance upconversion (UC) emission by producing two different coordination sites of trivalent cations in a matrix material and adjusting crystal field asymmetry by Hf⁴⁺ co-doping. A cubic phase, Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂, with these structural characteristics was synthesized successfully by introducing a small ion (Al³⁺) into YF₃. X-ray diffraction (XRD), nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), X-ray spectroscopy (XPS), and fluorescence spectrophotometry (FS) were employed for its crystalline structure and luminescent property analysis. As a result, the coordination environments of the rare-earth ions were varied more obviously than a hexagonal NaYF₄ matrix with the same Hf⁴⁺ co-doping concentration, with vertical comparison, UC luminescent intensities of cubic Y_3.2Al_0.32Yb_0.4Er_0.08F₁₂ were largely enhanced (∼32–80 times greater than that of different band emissions), while the maximum enhancement of hexagonal NaYF₄ was by a factor of ∼12. According to our experimental results, the mechanism has been demonstrated involving the crystalline structure, crystal field asymmetry, luminescence lifetime, hypersensitive transition, and so on. The study may be helpful for the design and fabrication of high-performance UC materials

Sensitized Near-Infrared Emission from Ir^III-Ln^III (Ln = Nd, Yb, Er) Bimetallic Complexes with a (N^∧O)(N^∧O) Bridging Ligand

A (N^∧O)­(N^∧O) bridging ligand, 5-bromopyrimidine-2-carboxylic acid (bpmc), was used for connecting Ir^III and Ln^III centers to construct the series of d–f bimetallic complexes Ir­(pdt)₂(μ-bpmc)­Ln­(TTA)₃, where pdt = 1,3-dimethyl-5-phenyl-1<i>H</i>-[1,2,4]­triazole, TTA = 4,4,4-trifluoro-1-(thiophen-2-yl)-butane-1,3-dionate, and Ln = Nd, Yb, Er, Gd. Crystallographic analyses reveal that there are very short spatial distances between the d–f centers (about 6 Å), and photophysical studies demonstrate the appropriate energy level of the Ir^III chromophore for sensitization of near-infrared (NIR) lanthanide ions, both of which are two important factors for efficient Ir^III → Ln^III energy transfer. The energy transfer rates for Ir^III-Nd^III, Ir^III-Yb^III, and Ir^III-Er^III are calculated to be 3.6 × 10⁹, 2.8 × 10⁸, and 4.0 × 10⁸ s^–1, respectively

Sensitized Near-Infrared Emission from Ir^III-Ln^III (Ln = Nd, Yb, Er) Bimetallic Complexes with a (N^∧O)(N^∧O) Bridging Ligand

A (N^∧O)­(N^∧O) bridging ligand, 5-bromopyrimidine-2-carboxylic acid (bpmc), was used for connecting Ir^III and Ln^III centers to construct the series of d–f bimetallic complexes Ir­(pdt)₂(μ-bpmc)­Ln­(TTA)₃, where pdt = 1,3-dimethyl-5-phenyl-1<i>H</i>-[1,2,4]­triazole, TTA = 4,4,4-trifluoro-1-(thiophen-2-yl)-butane-1,3-dionate, and Ln = Nd, Yb, Er, Gd. Crystallographic analyses reveal that there are very short spatial distances between the d–f centers (about 6 Å), and photophysical studies demonstrate the appropriate energy level of the Ir^III chromophore for sensitization of near-infrared (NIR) lanthanide ions, both of which are two important factors for efficient Ir^III → Ln^III energy transfer. The energy transfer rates for Ir^III-Nd^III, Ir^III-Yb^III, and Ir^III-Er^III are calculated to be 3.6 × 10⁹, 2.8 × 10⁸, and 4.0 × 10⁸ s^–1, respectively