Lanthanide(III)/pyrimidine-4,6-dicarboxylate/oxalate extended frameworks: a detailed study based on the lanthanide contraction and temperature effects

Detailed structural, magnetic, and luminescence studies of six different crystalline phases obtained in the lanthanide/pyrimidine-4,6-dicarboxylate/oxalate system have been afforded: {[Ln(μ-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·3H(2)O}(n) (1-Ln), {[Ln(μ-pmdc)(μ-ox)(0.5)(H(2)O)(3)]·2H(2)O}(n) (2-Ln), {[Ln(μ(3)-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·~2.33H(2)O}(n) (3-Ln), {[Ln(2)(μ(3)-pmdc)(μ(4)-pmdc)(μ-ox)(H(2)O)(3)]·5H(2)O}(n) (4-Ln), {[Ln(μ(3)-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·H(2)O}(n) (5-Ln), and [Ln(pmdc)(1.5)(H(2)O)(2.5)] (6-Ln). The slow generation of the oxalate (ox) anion, obtained from the in situ partial hydrothermal decomposition of the pyrimidine-4,6-dicarboxylate (pmdc) ligand, allows us to obtain good shaped single crystals, while direct addition of potassium oxalate provides the same compounds but as polycrystalline samples. The crystal structures of all compounds are based on the double chelation established by the pmdc and ox ligands to provide distorted 2D honeycomb layers that, in some cases, are fused together, leading to 3D systems, by replacing some of the coordinated water molecules that complete the coordination sphere of the lanthanide by uncoordinated carboxylate oxygen atoms of the pmdc. The presence of channels occupied by crystallization water molecules is also a common feature with the exception of compounds 5-Ln. It is worth noting that compounds 3-Ln present a commensurate crystal structure related to the partial occupancy of the crystallization water molecules placed within the channels. Topological analyses have been carried out, showing a previously nonregistered topology for compounds 4-Ln, named as jcr1. The crystal structures are strongly dependent on the lanthanide ion size and the temperature employed during the hydrothermal synthesis. The lanthanide contraction favors crystal structures involving sterically less hindranced coordination environments for the final members of the lanthanide series. Additionally, reinforcement of the entropic effects at high temperatures directs the crystallization process toward less hydrated crystal structures. The magnetic data of these compounds indicate that the exchange coupling between the lanthanide atoms is almost negligible, so the magnetic behavior is dominated by the spin-orbit coupling and the ligand field perturbation. The luminescence properties that exhibit the compounds containing Nd(III), Eu(III), and Tb(III) have been also characterized.     

Anti-stokes laser cooling in bulk erbium-doped materials

We report the first observation of anti-Stokes laser-induced cooling in the Er3+:KPb2Cl5 crystal and in the Er3+:CNBZn (CdF2-CdCl2-NaF-BaF2-BaCl2-ZnF2) glass. The internal cooling efficiencies have been calculated by using photothermal deflection spectroscopy. Thermal scans acquired with an infrared thermal camera proved the bulk cooling capability of the studied samples. The implications of these results are discussed.     

Near infrared to visible upconversion of Er in CaZrO3/CaSZ eutectic crystals with ordered lamellar microstructure

In this work we report the near infrared to visible upconversion luminescence of Er³⁺ ions in CaZrO₃/CaSZ eutectic crystals with ordered lamellar microstructure. The microstructure consists of alternating 2-μm-thick lamellae of calcia-stabilized zirconia (CaSZ) and calcium zirconate (CaZrO₃) single crystals. Er³⁺ ions enter both phases but at a higher concentration in CaSZ. Wavelength selective excitation along the ⁴I_15/2→⁴I_9/2 absorption band allows to distinguish the upconverted emission from Er³⁺ sites in the two eutectic phases. In the CaZrO₃ phase the upconversion emission spectrum is dominated by an intense green emission characterized by sharp (²H_11/2,⁴S_3/2) levels together with a more weak red emission from ⁴F_9/2 level. In the CaSZ phase, a broad green and red emissions occur with an enhancement of the red emission from level ⁴F_9/2. These upconverted emissions are attributed to a two photon process. The excitation wavelength dependence of the upconverted luminescence together with its time evolution after infrared pulsed excitation suggest that energy transfer upconversion processes are responsible for the upconversion luminescence.     

Spectroscopy of thulium and holmium heavily doped tellurite glasses

In this study, we report spectroscopic properties of Tm³⁺ and Ho³⁺ codoped tellurite glasses over a wide dopant concentration range in order to assess their potential laser performance under 790 nm diode laser excitation. The impact of Tm³⁺ and Ho³⁺ concentrations is investigated to identify specific candidates for fiber laser operation. The emission cross section is calculated and discussed, as well as the gain coefficient of this type of glasses. Energy transfer microparameters and critical ion distances are determined for ³H₄, ³F₄ (Tm³⁺), and ⁵I₇ (Ho³⁺) emission levels in the framework of diffusion-limited regime and dipole–dipole interaction. We also report thermal properties of tested glasses.     

Upconversion emission in Er<Superscript>3+</Superscript>-doped lead niobium germanate thin-film glasses produced by pulsed laser deposition

Thin films of Er³⁺-doped lead–niobium germanate have been produced by pulsed laser deposition from Er³⁺-doped 25PbO₂–25Nb₂O₅–50GeO₂ (mol%) transparent glasses with an Er content in the range 0.5–3 wt%. The room-temperature infrared to visible upconversion properties of these thin films have been investigated under 800-nm laser excitation. An energy transfer upconversion mechanism has been identified to be responsible for the population of the ⁴S_3/2:²H_11/2 excited level, from which an intense green emission occurs. A rate equation analysis supports the proposed mechanism.     

Study of lasing threshold and efficiency in laser crystal powders

We have analyzed theoretically the dependence of lasing threshold and efficiency of laser crystals powders on the sample thickness, the volume fraction occupied by the particles and the mean particle size. The optimal range of these parameters that minimize the threshold and maximize the efficiency has been determined.