Enhanced NIR Luminescence of Nanozeolite L Loading Lanthanide β‐Diketonate Complexes

Herein, we report the preparation of zeolite NIR luminescence materials with a remarkable increase of luminescence intensity by attaching stopper molecule (an imidazolium salt) to the channel entrances of zeolite L loading with NIR lanthanide (Er³⁺ or Nd³⁺) β‐diketonate complexes. This results from the formation of Ln³⁺‐β‐diketonate complexes (Ln=Er or Nd) with high coordination numbers through the decreasing of the proton strength in the zeolite channels. The obtained materials were characterized with SEM and photoluminescence spectroscopy. We believe that this hybrid material will be an appealing candidate for the applications of optical fiber, telecommunications and bio‐imaging.     

Rare‐Earth‐Based Nanoparticles with Simultaneously Enhanced Near‐Infrared (NIR)‐Visible (Vis) and NIR‐NIR Dual‐Conversion Luminescence for Multimodal Imaging

Multifunctional NaGdF₄:Yb³⁺,Er³⁺,Nd³⁺@NaGdF₄:Nd³⁺ core–shell nanoparticles (called Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:Nd³⁺ NPs) with simultaneously enhanced near‐infrared (NIR)‐visible (Vis) and NIR‐NIR dual‐conversion (up and down) luminescence (UCL/DCL) properties were successfully synthesized. The resulting core–shell NPs simultaneously emitted enhanced UCL at 522, 540, and 660 nm and DCL at 980 and 1060 nm under the excitation of a 793 nm laser. The enhanced UCL and DCL can be explained by complex energy‐transfer processes, Nd³⁺→Yb³⁺→Er³⁺ and Nd³⁺→Yb³⁺, respectively. The effects of Nd³⁺ concentration and shell thickness on the UCL/DCL properties were systematically investigated. The UCL and DCL properties of NPs were observed under the optimal conditions: a shell Nd³⁺ content of 20 % and a shell thickness of approximately 5 nm. Moreover, the Gd:Yb³⁺,Er³⁺,Nd³⁺@Gd:20 % Nd³⁺ NPs exhibited remarkable magnetic resonance imaging (MRI) properties similar to that of a clinical agent, Omniscan. Thus, the core–shell NPs with excellent UCL/DCL/magnetic resonance imaging (MRI) properties have great potential for both in vitro and in vivo multimodal bioimaging.     

DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-a:2′,3′-c]phenazine (dppz) Ligands: Synthesis,Crystal Structures,Stability, Luminescence Properties and CT-DNA Interaction

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO₃)₃(dppz)₂] (Ln = Nd³⁺, Er³⁺ and Yb³⁺; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce³⁺, Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Tm³⁺, Lu³⁺) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analysis of the complexes (Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Eu³⁺, Er³⁺, Yb³⁺, Lu³⁺) showed that the lanthanide’s first coordination sphere can be described as a bicapped dodecahedron, made up of two bidentate dppz ligands and three bidentate-coordinating nitrate anions. Efficient energy transfer was observed from the dppz ligand to the lanthanide ion (Nd³⁺, Er³⁺ and Yb³⁺), while relatively high luminescence lifetimes were detected for these complexes. In their excitation spectra, the maximum of the strong broad band is located at around 385 nm and this wavelength was further used for excitation of the chosen complexes. In their emission spectra, the following characteristic NIR emission peaks were observed: for a) Nd³⁺: ⁴F_3/2 → ⁴I_9/2 (870.8 nm), ⁴F_3/2 → ⁴I_11/2 (1052.7 nm) and ⁴F_3/2 → ⁴I_13/2 (1334.5 nm); b) Er³⁺: ⁴I_13/2 → ⁴I_15/2 (1529.0 nm) c) Yb³⁺: ²F_5/2 → ²F_7/2 (977.6 nm). While its low triplet energy level is ideally suited for efficient sensitization of Nd³⁺ and Er³⁺, the dppz ligand is considered not favorable as a sensitizer for most of the visible emitting lanthanide ions, due to its low-lying triplet level, which is too low for the accepting levels of most visible emitting lanthanides. Furthermore, the DNA intercalation ability of the [Nd(NO₃)₃(dppz)₂] complex with calf thymus DNA (CT-DNA) was confirmed using fluorescence spectroscopy.     

Ln3Q9 as a Molecular Framework for Ion‐Size‐Driven Assembly of Heterolanthanide (Nd,Er, Yb) Multiple Near‐Infrared Emitters

A unique example of discrete molecular entity Nd_yEr_xYb_3?(x+y)Q₉ ( 1 ) (Q=quinolinolato) containing three different lanthanides simultaneously emitting in three different spectral regions in the NIR, ranging from 900 to 1600 nm, has been synthesized and fully chararacterized. A simple molecular strategy based on tuning metal composition in the Ln₃Q₉ framework, which contains inequivalent central and terminal coordination sites, has allowed a satisfactory ion‐size‐driven control of molecular speciation close to 90 %. In 1 the central position of the larger Nd ion is well distinguished from the terminal ones of the smaller Yb³⁺ and Er³⁺, which are almost “vicariants” as found in the heterobimetallic Er_xYb_3?xQ₉ ( 2 ). The Ln₃Q₉ molecular architecture, which allows communication between the ions, has proved to afford multiple NIR emission in 1 and 2 , and is promising to develop a variety of multifunctional materials through the variation of the Ln composition.     

Complexation Properties of N,N′,N″,N′′′‐[1,4,7,10‐Tetraazacyclododecane‐1,4,7,10‐tetrayltetrakis(1‐oxoethane‐2,1‐diyl)]tetrakis[glycine] (H4dotagl). Equilibrium,Kinetic, and Relaxation Behavior of the Lanthanide(III) Complexes

Eu³⁺, Dy³⁺, and Yb³⁺ complexes of the dota‐derived tetramide N,N′,N″,N′′′‐[1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetrayltetrakis(1‐oxoethane‐2,1‐diyl)]tetrakis[glycine] (H₄dotagl) are potential CEST contrast agents in MRI. In the [Ln(dotagl)] complexes, the Ln³⁺ ion is in the cage formed by the four ring N‐atoms and the amide O‐atom donor atoms, and a H₂O molecule occupies the ninth coordination site. The stability constants of the [Ln(dotagl)] complexes are ca. 10 orders of magnitude lower than those of the [Ln(dota)] analogues (H₄dota=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The free carboxylate groups in [Ln(dotagl)] are protonated in the pH range 1–5, resulting in mono‐, di‐, tri‐, and tetraprotonated species. Complexes with divalent metals (Mg²⁺, Ca²⁺, and Cu²⁺) are also of relatively low stability. At pH>8, Cu²⁺ forms a hydroxo complex; however, the amide H‐atom(s) does not dissociate due to the absence of anchor N‐atom(s), which is the result of the rigid structure of the ring. The relaxivities of [Gd(dotagl)] decrease from 10 to 25°, then increase between 30–50°. This unusual trend is interpreted with the low H₂O‐exchange rate. The [Ln(dotagl)] complexes form slowly, via the equilibrium formation of a monoprotonated intermediate, which deprotonates and rearranges to the product in a slow, OH^?‐catalyzed reaction. The formation rates are lower than those for the corresponding Ln(dota) complexes. The dissociation rate of [Eu(dotagl)] is directly proportional to [H⁺] (0.1–1.0M HClO₄); the proton‐assisted dissociation rate is lower for [Eu(H₄dotagl)] (k₁=8.1?10^?6 M ^?1 s^?1) than for [Eu(dota)] (k₁=1.4?10^?5 M ^?1 s^?1).     

Infrared‐to‐Visible Light Conversion in Er3+–Yb3+:Lu3Ga5O12 Nanogarnets

Er³⁺–Yb³⁺ co‐doped Lu₃Ga₅O₁₂ nanogarnets were prepared and characterized; their structural and luminescence properties were determined as a function of the Yb³⁺ concentration. The morphology of the nanogarnets was studied by HRTEM. Under 488 nm excitation, the nanogarnets emit green, red, and near‐infrared light. The decay curves for the (⁴S_3/2, ²H_11/2) and ⁴F_9/2 levels of the Er³⁺ions exhibit a non‐exponential nature under resonant laser excitation and their effective lifetimes are found to decrease with an increase in the Yb³⁺ concentration from 1.0 to 10.0 mol %. The non‐exponential decay curves are well fitted to the Inokuti–Hirayama model for S=8, indicating that the mechanism of interaction for energy transfer between the optically active ions is of dipole–quadrupole type. Upon 976 nm laser excitation, an intense green upconverted emission is clearly observed by the naked eyes. A significant enhancement of the red‐to‐green intensity ratio of Er³⁺ ions was observed with an increase in Yb³⁺ concentration. The power dependence and the dynamics of the upconverted emission confirm the existence of two‐photon upconversion processes for the green and red emissions.     

ErxYb1-x(TPB)3Bath(x=0,0.218,0.799,0.896,0.987,1)配合物的近红外发光性能

采用4,4,4-三氟-1-苯基-1,3-丁二酮（TPB）为第一配体,4,7-二苯基-1,10-菲咯啉（Bath）为第二配体,分别制备了配合物Er（TPB）₃Bath和Yb（TPB）₃Bath,以及它们的混合配合物Er_xYb_1-x（TPB）₃Bath（x=0.218,0.799,0.896,0.987）,并对所制得配合物的发光性能进行了系统研究。研究结果表明,所有配合物均能发射所含稀土离子的近红外特征光,并且可以通过调节混合配合物中的n_Er/n_Yb来调控Yb³⁺/Er³⁺之间的能量传递,进而提高Er³⁺离子在1530 nm处的发光。     

Vibrational Quenching in Near-Infrared Emitting Lanthanide Complexes: A Quantitative Experimental Study and Novel Insights

Two series of novel NIR-emissive complexes of Nd³⁺, Sm³⁺, Er³⁺ and Yb³⁺ with two different β-diketonate ligands (L₁=4,4,4-trifluoro-1-phenyl-1,3-butadione and L₂=4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butadione) are reported. The neutral triphenylphosphine oxide (tppo) ligand was used to replace coordinated water molecules in the first coordination sphere of the as-obtained [Ln(L₁₍₂₎)₃(H₂O)₂] complexes to afford water-free [Ln(L₁₍₂₎)₃(tppo)₂] molecular species. Upon replacement of water molecules by tppo units, the NIR emission lifetimes of the Nd³⁺, Er³⁺and Sm³⁺complexes increase by about one order of magnitude up to values of ≈9, 8 and 113 ms while Yb³⁺ complexes reach intrinsic quantum yields as high as to Φ_Yb=6.5 %., which are remarkably high for fully hydrogenated complexes. Vibrational quenching by CH and OH oscillators has been quantitatively assessed by implementing the Förster's model of resonance energy transfer on the basis of experimental data. This study demonstrates that highly efficient NIR-emitting lanthanide complexes can be obtained with facile, cheap and accessible syntheses through a rational design.     

A general approach for selective enhancement of green upconversion emissions in Er3+ doped oxides by Yb3+–MoO4 2− dimer sensitizing

In this paper, we report a general approach to enhance the upconversion (UC) luminescence of Er³⁺ doped oxides phosphors by Yb³⁺–MoO₄ ^2? dimer sensitizing, which induced strong green UC emissions under the 976 nm laser diode excitation. By codoping of Yb³⁺ and Mo⁶⁺ in the Er³⁺ doped TiO₂ and ZnO, the green UC emissions intensity can be selectively increased about 10 and 500 times than those of Er³⁺–Yb³⁺ codoped TiO₂ and ZnO, respectively. The high excited state energy transfer between |²F_7/2, ³T₂> state of Yb³⁺–MoO₄ ^2? dimer and ⁴F_7/2 level of Er³⁺ significantly avoids the nonradiative decay processes happened at lower energy levels of Er³⁺, and then increases the green UC emissions efficiently. The proposed Yb³⁺–MoO₄ ^2? dimer sensitizing has been realized as an efficient way to enhance the green UC emissions in other Er³⁺ doped oxides phosphors. It is expected that the selective enhanced green UC emissions sensitized by Yb³⁺–MoO₄ ^2? dimer in Er³⁺ doped oxides phosphors can greatly extend their scope of applications.     

Synthesis,properties and mechanism of photodegradation of core–shell structured upconversion luminescent NaYF4:Yb3+,Er3+@BiOCl

Microspherical bismuth oxychloride (BiOCl) can only utilize ultraviolet (UV) light to promote photocatalytic reactions. To overcome this limitation, a uniform and thin BiOCl nanosheet was synthesized with a particle size of about 200 nm. As results of UV–visible diffuse reflectance spectroscopy showed, the band gap of this nanostructure was reduced to 2.78 eV, indicating that the BiOCl nanosheet could absorb and utilize visible light. Furthermore, the upconversion material NaYF₄ doped with rare earth ions Yb³⁺ and Er³⁺ emitted visible light at 410 nm following excitation with near‐infrared (NIR) light (980 nm), which could be utilized by BiOCl to produce a photocatalytic reaction. To produce a high‐efficiency photocatalyst (NaYF₄:Yb³⁺,Er³⁺@BiOCl), BiOCl‐loaded NaYF₄:Yb³⁺,Er³⁺ was successfully synthesized via a simple two‐step hydrothermal method. The as‐synthesized material was confirmed using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy as well as other characterizations. The removal ratio of methylene blue by NaYF₄:Yb³⁺,Er³⁺@BiOCl was much higher than that of BiOCl alone. Recycling experiments verified the stability of NaYF₄:Yb³⁺,Er³⁺@BiOCl, which demonstrated excellent adsorption, strong visible‐light absorption and high electron–hole separation efficiency. Such properties are expected to be useful in practical applications, and a further understanding of the NIR‐light‐responsive photocatalytic mechanism of this new catalytic material would be conducive to improving its structural design and function.     

Zur Kenntnis der Fluoride zweiwertiger Lanthanoide. III. Neue Fluoroperowskite vom Typ CsLn1−xLn′xF3 und RbLn1−xLn′xF3 mit Ln = Eu2+ bzw. Sm2+ und Ln′ = Yb2+

On Fluorides of Divalent Lanthanoids. III. New Fluoroperovskites of the MLn_1?xLn′_xF₃ Type with M = Cs, Rb; Ln = Eu²⁺, Sm²⁺; Ln′ Yb²⁺ New fluoroperovskites with divalent lanthanoids have been prepared. They are: CsEu_1?xYb_xF₃, yellow, with x = 0.25, a = 4.737(1) Å; x = 0.50, a = 4.696(1) Å; x = 0.75, a = 4.653(1) Å; CsSm_xYb_1?xF₃, violet, with x = 0.25, a = 4.656(1) Å; x = 0.18, a = 4.645(1) Å, the latter mixed with Sm_0.68Yb_0.32F₃, a = 5.781(1) Å; RbEu_xYb_1?xF₃, orange, with x = 0.25, a = 4.573(1) Å; x = 0.23, a = 4.568(1) Å, the latter mixed with Eu_0.94Yb_0.06F₂, a = 5.827(1) Å; RbSm_0.13Yb_0.87F₃, brown, a = 4.555(1) Å.     

Heterodinuclear Lanthanoid‐Containing Polyoxometalates: Stepwise Synthesis and Single‐Molecule Magnet Behavior

Polyoxometalates (POMs) with heterodinuclear lanthanoid cores, TBA₈H₄[{Ln(μ₂‐OH)₂Ln′}(γ‐SiW₁₀O₃₆)₂] ( LnLn′ ; Ln=Gd, Dy; Ln′=Eu, Yb, Lu; TBA=tetra‐n‐butylammonium), were successfully synthesized through the stepwise incorporation of two types of lanthanoid cations into the vacant sites of lacunary [γ‐SiW₁₀O₃₆]^8? units without the use of templating cations. The incorporation of a Ln³⁺ ion into the vacant site between two [γ‐SiW₁₀O₃₆]^8? units afforded mononuclear Ln³⁺‐containing sandwich‐type POMs with vacant sites ( Ln1 ; TBA₈H₅[{Ln(H₂O)₄}(γ‐SiW₁₀O₃₆)₂]; Ln=Dy, Gd, La). The vacant sites in Ln1 were surrounded by coordinating W? O and Ln? O oxygen atoms. On the addition of one equivalent of [Ln′(acac)₃] to solutions of Dy1 or Gd1 in 1,2‐dichloroethane (DCE), heterodinuclear lanthanoid cores with bis(μ₂‐OH) bridging ligands, [Dy(μ₂‐OH)₂Ln′]⁴⁺, were selectively synthesized ( LnLn′ ; Ln=Dy, Gd; Ln′=Eu, Yb, Lu). On the other hand, La1 , which contained the largest lanthanoid cation, could not accommodate a second Ln′³⁺ ion. DyLn′ showed single‐molecule magnet behavior and their energy barriers for magnetization reversal (ΔE/k_B) could be manipulated by adjusting the coordination geometry and anisotropy of the Dy³⁺ ion by tuning the adjacent Ln′³⁺ ion in the heterodinuclear [Dy(μ₂‐OH)₂Ln′]⁴⁺ cores. The energy barriers increased in the order: DyLu (ΔE/k_B=48 K)< DyYb (53 K)< DyDy (66 K)< DyEu (73 K), with an increase in the ionic radii of Ln′³⁺; DyEu showed the highest energy barrier.     

Synthesis and photophysical properties of Ir<Superscript>III</Superscript>-Ln<Superscript>III</Superscript> (Ln = Nd,Yb, Er) bimetallic complexes containing bipyrimidines as bridging ligands

Bipyrimidines have been chosen as (N∧N)(N∧N) bridging ligands for connecting metal centers. Ir^III-Ln^III (Ln = Nd, Yb, Er) bimetallic complexes [Ir(dfppy)₂(μ-bpm)Ln(TTA)₃]Cl were synthesized by using Ir(dfppy)₂(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)₃·2H₂O. The stability constants between Ir(dfppy)₂(bpm)Cl and lanthanide ions were measured by fluorescence titration. The obvious quenching of visible emission from Ir^III complex in the Ir^III-Ln^III (Ln = Nd, Yb, Er) bimetallic complexes indicates that energy transfer occurred from Ir^III center to lanthanides. NIR emissions from Nd^III, Yb^III, and Er^III were obtained under the excitation of visible light by selective excitation of the Ir^III-based chromophore. It was proven that Ir(dfppy)₂(bpm)Cl as the ligand could effectively sensitize NIR emission from Nd^III, Yb^III, and Er^III.     

Preparation and spectroscopic properties of nanostructured glass-ceramics containing Yb3+, Er3+ ions and Co2+-doped spinel nanocrystals

Transparent glass-ceramics with Yb³⁺, Er³⁺ ions in glass matrix and tetrahedral Co²⁺-doped MgAl₂O₄ nanocrystals were synthesized. XRD patterns and FESEM micrograph of the glass-ceramics showed that MgAl₂O₄ nanocrystals (sizes of 10–20 nm) are uniformly dispersed in SiO₂ glass matrix. Absorption and emission spectra of the glass-ceramics indicated that Yb³⁺, Er³⁺ remain in SiO₂ glass matrix, while Co²⁺ occupied tetrahedral sites in MgAl₂O₄ nanocrystals, and can function as saturable absorber for Er³⁺. Transparent Co²⁺, Yb³⁺, Er³⁺ co-doped glass-ceramics possesses the spectral requirements and should be a potential laser material used for self-Q-switched microchip laser operating at 1.5–1.6 μm.     

Bi3+‐Er3+ and Bi3+‐Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near‐Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f‐electron emission at 1540 nm (suitable for low‐loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺‐Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature‐dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Confining Excitation Energy in Er3+‐Sensitized Upconversion Nanocrystals through Tm3+‐Mediated Transient Energy Trapping

A new class of lanthanide‐doped upconversion nanoparticles are presented that are without Yb³⁺ or Nd³⁺ sensitizers in the host lattice. In erbium‐enriched core–shell NaErF₄:Tm (0.5 mol %)@NaYF₄ nanoparticles, a high degree of energy migration between Er³⁺ ions occurs to suppress the effect of concentration quenching upon surface coating. Unlike the conventional Yb³⁺‐Er³⁺ system, the Er³⁺ ion can serve as both the sensitizer and activator to enable an effective upconversion process. Importantly, an appropriate doping of Tm³⁺ has been demonstrated to further enhance upconversion luminescence through energy trapping. This endows the resultant nanoparticles with bright red (about 700‐fold enhancement) and near‐infrared luminescence that is achievable under multiple excitation wavelengths. This is a fundamental new pathway to mitigate the concentration quenching effect, thus offering a convenient method for red‐emitting upconversion nanoprobes for biological applications.     

Neue Vertreter des Er6[Si11N20]O‐Strukturtyps Hochtemperatur‐Synthesen und Kristallstrukturen von Ln(6+x/3)[Si(11–y)AlyN(20+x–y)]O(1–x+y) mit Ln = Nd,Er, Yb,Dy und 0 ≤ x ≤ 3, 0 ≤ y ≤ 3

New Representatives of the Er₆[Si₁₁N₂₀]O Structure Type. High‐Temperature Synthesis and Single‐Crystal Structure Refinement of Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) with Ln = Nd, Er, Yb, Dy and 0 ≤ x ≤ 3, 0 ≤ y ≤ 3 According to the general formula Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) (0 ≤ x ≤ 3, 0 ≤ y ≤ 3) four nitridosilicates, namely Er₆[Si₁₁N₂₀]O, Yb_6.081[Si₁₁N_20.234]O_0.757, Dy_0.33Sm₆[Si₁₁N₂₀]N, and Nd₇[Si₈Al₃N₂₀]O were synthesized in a radiofrequency furnace at temperatures between 1300 and 1650 °C. The homeotypic crystal structures of all four compounds were determined by single‐crystal X‐ray diffraction. The nitridosilicates are trigonal with the following lattice constants: Er₆[Si₁₁N₂₀]O: a = 978.8(4) pm, c = 1058.8(3) pm; Yb_6.081[Si₁₁N_20.243]O_0.757: a = 974.9(1) pm, c = 1055.7(2) pm; Dy_0.33Sm₆[Si₁₁N₂₀]N: a = 989.8(1) pm, c = 1078.7(1) pm; Nd₇[Si₈Al₃N₂₀]O: a = 1004.25(9) pm, c = 1095.03(12) pm. The crystal structures were solved and refined in the space group P31c with Z = 2. The compounds contain three‐dimensional networks built up by corner sharing SiN₄ and AlN₄ tetrahedra, respectively. The Ln³⁺ and the “isolated” O^2– ions are situated in the voids of the structures. According to Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) an extension of the Er₆[Si₁₁N₂₀]O structure type has been found.     

PMLABe Diol Synthesized by Ring‐Opening Polymerization of Racemic Benzyl β‐Malolactonate Initiated by Rare‐Earth Trisborohydride Complexes: An Experimental and DFT Study

Polymer diols are a class of polymeric building blocks of high interest for the synthesis of complex macromolecular edifices. Rare‐earth borohydride complexes are known as efficient initiators for the ring‐opening polymerization (ROP) of cyclic esters, directly affording α,ω‐dihydroxy‐telechelic polyesters. Here, were report the direct synthesis of poly(benzyl β‐malolactonate) (PMLABe) diols, from the ROP of racemic (benzyl β‐malolactonate) (rac‐MLABe), a valuable and renewable monomer, initiated by the homoleptic [Ln(BH₄)₃(thf)₃] (Ln=La, Nd, and Sm) complexes. These initiators enabled the controlled ROP of this β‐lactone, affording well‐defined syndiotactic‐enriched (P_r≈0.83) PMLABes (M_n up to 21 300 g mol^?1, Ð_M≈1.5) as evidenced by size exclusion chromatography, ¹H and ¹³C NMR spectroscopy, and MALDI‐ToF mass spectrometry analyses. The first and second insertions of rac‐MLABe, as assessed by DFT calculations, revealed more favorable stationary front‐side than migratory back‐side insertions, the thermodynamically and kinetically competitive ROP on two distinct arms with that on a one arm‐only, and the thermodynamically slightly favored formation of syndiotactic‐enriched PMLABes.     

Synthesis and Infrared Multi‐band Absorption Properties of Core‐shell NaYF4:Yb3+, Er3+@SiO2 Nanoparticles

Due to the unique size effects, nanomaterials in infrared absorption have attracted much attention for their strong absorption in the infrared region. To achieve the infrared multi‐band absorption, we propose to synthesize a core‐shell structure nanomaterial consisting of NaYF₄:Yb³⁺, Er³⁺ core and a layer of SiO₂ as shell. A series of NaYF₄:Yb³⁺, Er³⁺ nanocrystals were synthesized through hydrothermal method by adjusting the ratio of citric acid(CA)‐to‐NaOH, and the effects of CA concentration, and NaOH concentration were studied in detail. NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were synthesized by sol‐gel method using TEOS as silica source. The results show that the core‐shell NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were successfully synthesized. Up‐conversion spectra of these nanoparticles were recorded with 980 nm laser excitation under room temperature. There are no changes of the emission centers of nanoparticles before or after silica coating, but the emission intensities of nanoparticles after silica coating are weakened. Furthermore, the property of infrared multi‐band absorption was tested through ultraviolet‐visible‐near infrared spectrophotometer and infrared absorption spectra. The results illustrate that the multi‐band infrared absorption nanomaterial was successfully synthesized.     

One‐Step Synthesis of Small‐Sized and Water‐Soluble NaREF4 Upconversion Nanoparticles for In Vitro Cell Imaging and Drug Delivery

Small (2–28 nm) NaREF₄ (rare earth (RE)=Nd–Lu, Y) nanoparticles (NPs) were prepared by an oil/water two‐phase approach. Meanwhile, hydrophilic NPs can be obtained through a successful phase‐transition process by introducing the amphiphilic surfactant sodium dodecylsulfate (SDS) into the same reaction system. Hollow‐structured NaREF₄ (RE=Y, Yb, Lu) NPs can be fabricated in situ by electron‐beam lithography on solid NPs. The MTT assay indicates that these hydrophilic NPs with hollow structures exhibit good biocompatibility. The as‐prepared hollow‐structured NPs can be used as anti‐cancer drug carriers for drug storage/release investigations. Doxorubicin hydrochloride (DOX) was taken as model drug. The release of DOX from hollow α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ exhibits a pH‐sensitive release patterns. Confocal microscopy observations indicate that the NPs can be taken up by HeLa cells and show obvious anti‐cancer efficacy. Furthermore, α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ NPs show bright‐red emission under IR excitation, making both the excitation and emission light fall within the “optical window” of biological tissues. The application of α‐NaLuF₄:20 % Yb³⁺, 2 % Er³⁺ in the luminescence imaging of cells was also investigated, which shows a bright‐red emission without background noise.