Rare Earth Metal Ions Research Articles

Dynamic Rare-Earth Metal-Organic Frameworks Based on Molecular Rotor Linkers with Efficient Emissions and Ultrasensitive Optical Sensing Performance.

4,4',4″-Triphenylamine tricarboxylate (TPA-COOH) with a distinct molecular rotor structure was reacted with rare-earth (RE) metal ions to obtain seven dynamic RE-based luminescent MOFs (RE-LMOFs) (i.e., emission colors in the blue, yellow-green, red, and near-infrared regions and emission peak wavelengths between 400 and 1600 nm) via the effective transfer of absorbed energy from TPA-COOH to the RE metal ions through the antenna effect. Due to the large energy level difference between RE ions, it was rare in the early days to use the same ligand to construct energy-level matching RE-LMOF homologues with multiple RE metal centers. The uncoordinated oxygen atoms on the molecular rotor linkers in RE-LMOFs provide active sites that can specifically capture highly toxic metal ions and strong oxidative pollutants. The limit of detection (LOD) of RE-LMOF for Al(III) ions is far below the maximum concentration of Al(III) ions in drinking water stipulated by the U.S. Environmental Protection Agency (USEPA) and that for H2O2 is much lower than the H2O2 content in cancer cells, showing excellent application potential for diagnosing early cell cancelation.

Terahertz Crystal-Field Transitions and Quasi Ferromagnetic Magnon Excitations in a Noncollinear Magnet for Hybrid Spin-Wave Computation.

The complexity of interactions between the crystal-field and unusual noncollinear spin arrangement in nontrivial magnets demands novel tools to unravel the mystery underneath. In this work, we study such interaction dynamics of crystal-field excitations (CFE) and low-energy magnetic excitations in orthochromite TmCrO3 with controls of temperature and magnetic field using high-resolution magneto-terahertz (THz) time-domain spectroscopy. The THz energy spectrum spanning 0.5-10 meV possesses a low-frequency spin-excitation (magnon) mode and a multitude of CFE modes at 10 K, all of which uniquely embody a range of phenomena. For the magnon mode, a temperature dependence of peak frequency is induced by magnetic interactions between Tm and Cr subsystems. While a change from blue to red shift of peak frequency of this mode marks the magnetization reversal transition, the spin-reorientation temperature and change of magnetic anisotropy are depicted by different features of field and temperature dependent peak frequency dynamics. The modes corresponding to CFE are robust and laden with a multitude of submodes, which are attributes of nontrivial interactions across different transitions. These modes are suppressed only upon substitution of Tb3+ at the Tm3+ site, which suggests a dominant role of single-ion anisotropy in controlling entire THz excitation spectra. Overall, this remarkable range of phenomena seen through the unique lens of all-optical THz tools provides deeper insights into the origin of magnetic phases in systems with complex interactions between rare-earth and transition metal ions and provides a multitude of novel combinations of closely spaced modes for emerging hybrid spin-wave computation.

Modification of microstructural, mechanical and optical properties with carbon ion irradiation in Y2SiO5 crystals

Yttrium orthosilicate Y2SiO5 crystals, a member of the silicate family, are versatile and multifunctional materials when doped with rare earth or transition metal ions. However, there have been limited investigations into the impact of ion irradiation on the crystal structure of Y2SiO5 crystals to date. In this paper, the effect of microstructure, mechanical and optical properties of Y2SiO5 crystal before and after different fluences of carbon ions irradiation was investigated utilizing complementary characterization techniques. The results indicate that carbon ion irradiation caused lattice disorder and damage, which resulted in structural deterioration and changes in optical properties, such as decrease in the optical band gap energy (from5.77 eV to 5.44 eV), changes in the effective refractive index (neff) which resulted in the formation of “well + barrier” type and “barrier” type waveguides. In addition, elastic modulus increased after carbon ion irradiation. The results will be helpful for understanding the damage study of the Y2SiO5 crystal with carbon ion irradiation and proving that ion beam techniques can be used for material modification.

Investigation of rare earth metal ions (Sm and Er) doped CoMoO4 polymorphs for photocatalytic dye degradation

Cobalt molybdate (CoMoO4) and its rare earth doped variants have emerged as promising photocatalysts for degrading dye pollutants in wastewater. The photocatalysts were prepared using a modified sol-gel method, employing ammonium heptamolybdate tetrahydrate and cobalt (II) nitrate hexahydrate as precursors. The incorporation of samarium and erbium as a dopant was hypothesized to improve the photocatalytic activity of CoMoO4 by altering its band structure and creating defect sites for improved dye adsorption and degradation. The structural and optical properties of the synthesized photocatalysts were characterized using various techniques. The photocatalytic performance of CoMoO4, Sm:CoMoO4 and Er:CoMoO4 was evaluated by monitoring the degradation of MB dye under light irradiation. The results reveal that Sm:CoMoO4 and Er:CoMoO4 catalysts achieve a degradation efficiencies of 99 % and 97 %, respectively, highlighting the potential of rare earth-doped CoMoO4 as an efficient photocatalyst for the remediation of dye contaminated wastewater.

Enhanced hypersensitive (5D0→7F2) transition characteristics of Eu3+ doped β-Ga2O3 microrods

Exploring and realizing the luminescence characteristics of rare earth metal (RE) ions doped gallium oxide (Ga2O3) is crucial for developing optoelectronic device applications. The current research used the solid-state reaction approach to synthesize Ga2O3 microrods doped with various europium (Eu3+) concentrations (0.1, 0.2, 0.3, 0.5, 0.75, and 1 mol). X-ray diffraction (XRD) and Raman spectral analyses confirm the monoclinic structure of β-Ga2O3. The intensity of the Raman phonon modes decreased and a peak shift was observed for Eu:β-Ga2O3. The electron microscopy (SEM, TEM) images depicted a nearly uniform distribution of microrods for undoped and Eu:β-Ga2O3 samples. The interplanar distance (d = 0.290 nm, 0.561 nm, and 0.433 nm), from HR-TEM images, corresponding to (0 0 4), (1 0 0), and (1 0 2) crystallographic orientations confirm the monoclinic structure of β-Ga2O3. The elemental mapping images showed a nearly homogeneous Ga, O, and Eu distribution. The UV–visible diffuse reflectance spectroscopy (UV-DRS) showed a notable reduction in the bandgap as the Eu3+ concentration increased. The emission spectra of Eu: β-Ga2O3 microrods showed a narrow red emission at 612 nm (5D0 → 7F2), which relates to the 5D0 → 7Fj (j = 0, 1, 2, 3) energy level arising from an intra-4f transition of Eu3+ ions upon 394 and 465 nm excitation. The red emission was found to increase with Eu content up to 0.5 mol.%. A quenching of emission due to the multipole–multipole interactions was obtained beyond 0.5 mol.% of Eu. The absolute quantum yield (η) calculated for Eu: β-Ga2O3 (0.5 mol.%) was 3.82 %. The luminescence decay curve using the bi-exponential fit and the average lifetime (τ) of the Eu: β-Ga2O3 (0.5 mol.%) was found to be ∼0.172 ms. CIE chromaticity and correlated color temperature analyses of Eu:β-Ga2O3 microrods yielded a red emission with a superior color purity (93 %). The obtained results suggest that Eu:β-Ga2O3 (0.5 wt.%) microrods could be one of the potential candidates for red light sources.

Broad spectral response of Y-NaBi(MoO4)2@NaYF4:Yb, Tm photocatalysts for efficient degradation of ciprofloxacin: Upconversion mechanism and theoretical calculations

In this work, a novel Y-NaBi(MoO4)2@NaYF4:Yb, Tm composite was successfully synthesized for the first time by hydrothermal method. The lamellar Y-NaBi(MoO4)2 was dispersed on the surface of the hexagonal prism NaYF4:Yb, Tm without aggregation. The composite achieved a broad spectral response. The NaYF4:Yb, Tm absorbed near-infrared light and emitted ultraviolet and visible light by the energy transfer upconversion process. The emitted light was reabsorbed by Y-NaBi(MoO4)2 through the fluorescence resonance energy transfer process. Moreover, the doping of Y3+ ions enhanced the light response capability of the composite. The experimental results revealed that the photocatalytic degradation efficiency of ciprofloxacin (CIP) reached 96.2 % after 180 min of illumination under simulated sunlight. Meanwhile, the degradation pathways and attack sites of CIP were intensively investigated by liquid chromatography-mass spectrometry analysis and density functional theory theoretical calculations. The upconversion process, the separation of photogenerated carriers and rare earth metal ion doping all contributed to the high effective photodegradation. This work provided a new strategy for effective utilization of solar energy for the degradation of emerging pollutants to mitigate environmental pollution.

Membrane transport of rare earth metal ions N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane by the active transport mechanism

The method of membrane extraction for rare earth elements (REE) using the carrier N, N’-bisdioctylphosphorylmethyl-1,4-diaminobutane (DPDA-8) ions, leveraging an active transport mechanism, has been optimized. The distribution of DPDA-8 within the membrane pores was confirmed using scanning electron microscopy (SEM). Both light and heavy REE extractions from a simulated solution using DPDA-8 and trioctylphosphine oxide (TOPO) in 1,2-dichlorobenzene were explored. The influence of feed solution pH, carrier and anion concentration, supported liquid membrane (SLM) type and stability, and cell temperature, among other parameters, were meticulously examined. The results indicate a decrease in permeability with a decrease in feed solution pH attributed to competitive acid transport through the membrane. Additionally, the formation of H-complexes between carriers and perchloric or phosphoric acids was investigated using Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. Changes in the stretching bands of amino and phosphine oxide groups in DPDA-8 were monitored and characterized. XRD analysis of the crystal structures of salts DPDA-6·ClO4 and DPDA-12·H2PO4 revealed a two-dimensional layered supramolecular organization with varying anion positions relative to hydrophobic fragments. The DPDA-8 carrier demonstrated significantly higher permeability values compared to TOPO, with differences in permeability exceeding twofold for certain metals. FTIR spectroscopy identified the main coordination centers of DPDA-8 during the liquid–liquid extraction of specific REEs.

Cerium rare-earth ions reinforced built-in electric field to enable efficient carrier extraction for highly efficient and stable perovskite solar cells

Perovskite solar cells prepared by inorganic-organic three-dimensional hybrid have good power conversion efficiency, but their operational stability remains a major challenge for commercialization. The defect of perovskite is an important factor restricting its charge dynamics and stability. Here, the rare earth metal chloride CeCl3 is introduced into perovskite solution to passivate the defects, where the Pb2+ part of the B position is replaced by Ce3+. The prepared films have the characteristics of increasing grain size, enhancing carrier mobility and excellent crystallinity. Meanwhile, via passivating interface defects and improving carrier transport capacity, the generation of non-radiative recombination is reduced, the carrier migration length is extended, and the device performance is improved. The results show that the PCE of the standard device is only 65 % after 2880 h of N2 atmosphere at room temperature, while the efficiency of the device doped with CeCl3 can remain at 93 %. When the unencapsulated sample was placed in an air environment (40–60 % humidity), the control sample was reduced to 72 % at 1060 h, while the CeCl3 was maintained at 87 %. Additionally, the reduction of residual stress in the perovskite layer also provides good bending stability for the flexible target device. These results show that the incorporation of rare earth metal ions is an effective way to stabilize and improve the efficiency of the device.

(Ce, Nd) co-doped TiO2 NPs via hydrothermal route:Structural, optical, photocatalytic and thermal behavior

Rare earth (Ce, Nd) doped/co-doped titania (TiO2) nanoparticles were successfully produced by hydrothermal route. Titanium isopropoxide (IV), cerium nitrate hexahydrate and neodymium nitrate hexahydrate were utilized as raw/starting materials. The effect of Ce and Nd doping/co-doping in TiO2 were studied through different complementary tools such as XRD, FTIR, FE-SEM, EDX, XPS, UV–Visible, PL, photocatalytic and thermal analysis. XRD spectra revealed anatase tetragonal phase and cubic phase due to titania and ceria nanoparticles respectively. The crystallite size, lattice constants, volume and no. of unit cell were determined through XRD data. Optical studies revealed the band gap, urbach energy, extinction coefficient, refractive index, optical conductivity and photoluminescence emission wavelength. FTIR spectra investigated the chemical bondings and functional groups present in prepared samples. Optical absorption spectra confirmed that absorption edge is red shifted, indicating a decrease in band gap from 3.5 to 3.0 eV with the incorporation of rare earth ions (Ce, Nd) in TiO2 matrix. The rate of electron-hole pair recombination was reduced through co-doping of (Ce, Nd) in TiO2 lattice as exhibited by reduction in intensity of photo luminescence spectra. The photocatalytic efficiency was enhanced with the integration of rare earth metal ions in TiO2 matrix for different dyes such as rhodamine B (RhB) and malachite green (MG) with visible light irradiation. The degradation efficiency of (Ce, Nd) co-doped TiO2 NPs against RhB and MG dyes was found to be 89 and 95 % respectively. TGA analysis was carried out to find weight loss during different thermodynamic phases such as dehydration, decomposition and combustion, and crystallization. Various thermodynamic parameters such as activation energy, entropy and enthalpy were estimated by thermal analysis.

Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites.

Materials with near-infrared (near-IR) luminescence are desirable for applications in communications and sensing, as well as biomedical diagnostics and imaging. The most used inorganic near-IR emitters rely on precise doping of host crystal structures with select rare-earth or transition metal ions. Recently, another class of materials with intrinsic near-IR emission has been reported. The compositions of these materials were initially described as vacancy-ordered halide double perovskites Cs2MoCl6 and Cs2WCl6, but further investigation by some of us on the compound reported as Cs2WCl6 revealed an oxyhalide instead, with a composition Cs2WO x Cl6-x , where 1 < x < 2. Here we demonstrate that the Mo compounds similarly possess the composition Cs2MoO x Cl6-x or Cs2MoO x Br6-x where 1 < x < 2. Preparing the pure halide appears harder for Mo than for W, and we have not succeeded in doing so. The distinctly different composition requires the coordination environment and oxidation state for the Mo and W centers to be reconsidered from what was assumed for the pure halides. In this work, we examine the mechanism for near-IR emission in these materials given their true structures and compositions. We demonstrate that the luminescence is due to the specific d-orbital splitting caused by the presence of oxygen in the distorted [MOX5]2- octahedra (X is Cl or Br). The fine structure in the emission spectra at low temperatures has been resolved and is attributed to vibronic coupling to the Mo-O and W-O bond stretches. Understanding the true structure and composition of these interesting materials, besides explaining the near-IR luminescence, suggests how this desirable emission can be realized and manipulated.

Environmentally friendly non-saponification solvent extraction and separation process for RE(III) (RE = Eu, Gd and Tb) in acetic acid solution using HEHEHP/n-heptane

The key to achieving sustainable metal extraction development is to avoid the generation of high-salt wastewater from the source. Here, a new system for the extraction and separation of lanthanide elements Eu(III), Gd(III) and Tb(III) from the acetic acid solution using HEHEHP (2-ethylhexyl hydrogen-2-ethylhexylphosphonate) was studied. The corresponding parameters including contact time, HEHEHP concentration, concentrations of rare earth metal ions and acetic acid in the initial solution, aqueous/organic phase volume ratio (R(A/O)), and temperature were considered to optimize the conditions for the separation of different rare earth elements. The results showed that the separation coefficients of Tb(III)/Gd(III) and Gd(III)/Eu(III) in the acetic acid system were approximately 6.2 and 1.7, with HEHEHP of 0.15 mol/L and R(A/O) of 2:1, and the extraction efficiency of RE(III) reached approximately 73.1%, which was higher than that in the hydrochloric acid and sulfuric acid systems. The mechanism associated with the extraction reaction was evaluated and discussed by the maximum loading capacity method, chromatographic analysis, and FT-IR spectrometric analysis. The mechanism followed a cation exchange reaction and acetic acid did not participate in the extraction process. The feasibility of the separation of Tb(III) from Eu(III) and Gd(III)was also given in terms of the separation coefficients between different elements at different extraction conditions. Since saponification is not necessary in the acetic acid extraction system, it can considerably reduce wastewater discharge to the ecological environment from the source.

Modern Rare Earth Imprinted Membranes for the Recovery of Rare Earth Metal Ions from Coal Fly Ash Extracts.

The need to identify secondary sources of REEs and their recovery has led to the search for new methods and materials. In this study, a novel type of ion-imprinted adsorption membranes based on modified chitosan was synthesized. Their application for the recovery of chosen REEs from synthetic coal fly ash extracts was analyzed. The examined membranes were analyzed in terms of adsorption kinetics, isotherms, selectivity, reuse, and their separation abilities. The experimental data obtained were analyzed with two applications, namely, REE 2.0 and REE_isotherm. It was found that the adsorption of Nd3+ and Y3+ ions in the obtained membranes took place according to the chemisorption mechanism and was significantly controlled by film diffusion. The binding sites on the adsorbent surface were uniformly distributed; the examined ions showed the features of regular monolayer adsorption; and the adsorbents showed a strong affinity to the REE ions. The high values of Kd (900-1472.8 mL/g) demonstrate their high efficiency in the recovery of REEs. After five subsequent adsorption-desorption processes, approximately 85% of the value of one cycle was reached. The synthesized membranes showed a high rejection of the matrix components (Na, Mg, Ca, Al, Fe, and Si) in the extracts of the coal fly ashes, and the retention ratio for these Nd and Y ions was 90.11% and 80.95%, respectively.

Near-Infrared Luminescent Materials Incorporating Rare Earth/Transition Metal Ions: From Materials to Applications.

The spotlight has shifted to near-infrared (NIR) luminescent materials emitting beyond 1000 nm, with growing interest due to their unique characteristics. The ability of NIR-II emission (1000-1700 nm) to penetrate deeply and transmit independently positions these NIR luminescent materials for applications in optical-communication devices, bioimaging, and photodetectors. The combination of rare earth metals/transition metals with a variety of matrix materials provides a new platform for creating new chemical and physical properties for materials science and device applications. In this review, the recent advancements in NIR emission activated by rare earth and transition metal ions are summarized and their role in applications spanning bioimaging, sensing, and optoelectronics is illustrated. It started with various synthesis techniques and explored how rare earths/transition metals can be skillfully incorporated into various matrixes, thereby endowing them with unique characteristics. The discussion to strategies of enhancing excitation absorption and emission efficiency, spotlighting innovations like dye sensitization and surface plasmon resonance effects is then extended. Subsequently, a significant focus is placed on functionalization strategies and their applications. Finally, a comprehensive analysis of the challenges and proposed strategies for rare earth/transition metal ion-doped near-infrared luminescent materials, summarizing the insights of each section is provided.

Preparation of a class of cucurbit[6]uril-light rare-earth-based supramolecular assemblies and its efficient detection of chloramphenicol

By introducing 4,4′-naphthalenedisulfonic acid (4,4′-H2BPs) as a structure-induced agent, four novel cucurbit[6]uril-based supramolecular assemblies have been successfully prepared in the cucurbit[6]uril (Q[6]) system with light rare-earth elements (La3+, Ce3+, Pr3+, Nd3+) under hydrothermal conditions. Crystal structure analysis shows that the assemblies 1 (La3+), 2 (Ce3+), 3 (Pr3+) are isomorphism 3D frameworks, where Q[6] can directly coordinate with light rare-earth metal ions to form 1D −Ln(III)- Q[6]-Ln(III)- chains, while the 4 (Nd3+) presents 3D structures stacking by the unit of Q[6]@Nd3+@Q[6]@Nd3+@Q[6], respectively. In these structures, 4,4′-H2BPs ligands all can act as an organic counter anion and bridging via the outer-surface interaction of cucurbit[n]uril (OSIQ) in the system, which is the main driving force from low-dimensional to high-dimensional. Meanwhile, the fluorescence sensing performance of the two assemblies for antibiotics was investigated, and the results showed that assembly 1 could be used as a promising fluorescent sensor material to detect chloramphenicol (CAP).

An insight into the co-doping effect of d-d transitions of transition metal ions and hypersensitivity of rare-earth ions in multicomponent glass-system

A multicomponent glass system with composition (70B2O3-22.5Bi2O3-5SeO2-2CuO-0.5Sm2O3) was synthesized via the conventional melt-quench technique. X-ray diffraction analysis confirmed the amorphous nature of this glass. The co-doping of transition and rare-earth metal ions results in the gradual decrease in glass transition temperature and improvement in thermal stability as observed from differential scanning calorimetry. The addition of CuO has increased non-bridging oxygens in multicomponent glass system. The increase in non-bridging oxygens results in a decrease in the optical band gap energy of the glass. Various results reveal that the hypersensitive nature of rare-earth ions has been suppressed by the d-d transition. A decrease in the energy band gap upon co-doping of transition and rare earth ions, suggests its applications in the fields of optoelectronics.

Ultrafast photoluminescence and multiscale light amplification in nanoplasmonic cavity glass.

Interactions between plasmons and exciton nanoemitters in plexcitonic systems lead to fast and intense luminescence, desirable in optoelectonic devices, ultrafast optical switches and quantum information science. While luminescence enhancement through exciton-plasmon coupling has thus far been mostly demonstrated in micro- and nanoscale structures, analogous demonstrations in bulk materials have been largely neglected. Here we present a bulk nanocomposite glass doped with cadmium telluride quantum dots (CdTe QDs) and silver nanoparticles, nAg, which act as exciton and plasmon sources, respectively. This glass exhibits ultranarrow, FWHM = 13 nm, and ultrafast, 90 ps, amplified photoluminescence (PL), λem≅503 nm, at room temperature under continuous-wave excitation, λexc = 405 nm. Numerical simulations confirm that the observed improvement in emission is a result of a multiscale light enhancement owing to the ensemble of QD-populated plasmonic nanocavities in the material. Power-dependent measurements indicate that >100 mW coherent light amplification occurs. These types of bulk plasmon-exciton composites could be designed comprising a plethora of components/functionalities, including emitters (QDs, rare earth and transition metal ions) and nanoplasmonic elements (Ag/Au/TCO, spherical/anisotropic/miscellaneous), to achieve targeted applications.

Metal-Assisted Injection Spinning of Ultra Strong Fibers from Megamolecular LC Polysaccharides.

The molecular orientation of liquid crystalline (LC) hydrogels has the potential to induce a range of functionalities that can deliver great mechanical strength. Sacran is a supergiant LC polysaccharide isolated from the cyanobacterium Aphanothece sacrum with a high amount of anionic functional groups such as sulfates and carboxylates. In this article, ultra-strong sacran hydrogels and their dried fibers were produced by cross-linking under injection flow with trivalent metal ions such as Al3+, Cr3+, Fe3+, In3+, and rare-earth metal ions such Er3+ and Sr3+. Crossed-polarizing microscopy and X-ray diffraction imaging revealed a uniaxial molecular orientation in the LC gel fiber, resulting in outstanding mechanical characteristics.

Synergistic effect of Li, La co-doping on photocatalytic activity of BaTiO3 ferroelectric material for effective degradation of toxic NOx for environmental remediation

We investigated the synergistic effects of Li, La-doping and co-doping on the A-site of perovskite BaTiO3 microstructure as a catalyst for the removal of toxic NOx for environmental remediation. The Rietveld refinement of XRD and Raman analysis confirmed that at room temperature, the ceramic samples possessed a pure-tetragonal perovskite structure, with P4mm space group. SEM images revealed a denser microstructure with reduced grain size on Li, La doping in BaTiO3. XPS results confirmed the coexistence of Li and La as doping elements into BaTiO3 lattice. EPR and PL spectra demonstrate the presence of Ti and Ba vacancies as well as defects. According to the DRS results, the absorption edge of the co-doped sample was blue-shifted. In frequency-dependent dielectrics, the co-doped sample exhibits the greatest rise in dielectric permittivity. Impedance measurement demonstrates the fastest rate of charge transport in Ba0.98Li0.01La0.01TiO3. Similarly, Li and La incorporation into BaTiO3 significantly reduced the recombination extent of charge carriers as evidenced by the PL. Under UV light, the photocatalytic NOx degradation with Ba0.98Li0.01La0.01TiO3 achieved a remarkable 44 % efficiency during 60 min. This enhancement is associated with improved charge carrier separation at the interface between the ferroelectric surfaces. Only a marginal decrease in photocatalytic activity occurred after four consecutive runs. A reasonable photocatalytic mechanism for the degradation of NOx over Ba0.98Li0.01La0.01TiO3 is proposed. This study's findings can inspire the design and synthesis of rare earth and alkali metal ion co-doped photocatalysts with built-in electric fields of a ferroelectric material for efficient NOx removal from the environment.

Synthesis, structure, fluorescence and magnetic studies of two oxygen bridged polycarboxylic acid ligands and rare earth metal ion Pr, Gd, and Er complexes

In order to further enrich the research on the synthesis of complexes with polycarboxylic acid ligands and rare earth metal ion. In this study, four rare earth complexes, namely, [Gd(cpia)]n (1), [Er(cpia)]n (2), [Pr(cpna)2·2H2O]n (3) and [Gd(Hcpna)(cpna)•3H2O]n (4) have been synthesized by solvothermal method based on 5-(2-carboxyphenoxy)isophthalic acid (H3cpia) and 5-(4-carboxyphenoxy)nicotinic acid ligand (H2cpna) with rare earth metal ions Pr3+, Gd3+ and Er3+. Single crystal X-ray diffraction analyses reveal that complexes 1, 2 and 3 are two-dimensional network structure, 4 is one-dimensional chain structures. The fluorescence test results show that the fluorescence intensity of complexes 1 and 2 were lower than that of the H3cpia ligand, the fluorescence intensity of complexes 3 and 4 were lower than that of the H2cpna ligand. Magnetic results indicate complex 1 has ferromagentic behavior and weak antiferromagentic behavior in the complexes 2, 3 and 4.

Infrared nonlinear optical materials with multiple strongly ionic cations

Infrared nonlinear optical (IR-NLO) crystals with excellent properties are in extensive demand due to their important role in IR laser technology. Currently, it remains a great challenge to obtain IR-NLO materials with both high second harmonic generation (SHG) response and large laser-induced damage thresholds (LIDTs). Some structural design strategies such as ‘structural/functional regions’ have been adopted to develop new high-performance NLO materials. The covalent structural region producing SHG signals has been extensively investigated, whereas the hard cations (alkali, alkaline-earth, and rare-earth metal ions) which are responsible for improving LIDTs, have been relatively neglected. Utilizing the concept of structural/functional regions, we focus on the relation between structural regions and SHG properties in chalcogenides. Combining different kinds of hard cations can change the dimension of structures and affect the stacking of NLO-active groups. Introducing more hard cations and constructing more complex ion regions help to increase the laser damage threshold. Based on the mentioned structural strategies, guidance will be provided for developing high-performance multiple-cation materials for IR NLO applications.