Luminescent κ-Carrageenan-Based Electrolytes Containing Neodymium Triflate.

In recent years, the synthesis of polymer electrolyte systems derived from biopolymers for the development of sustainable green electrochemical devices has attracted great attention. Here electrolytes based on the red seaweeds-derived polysaccharide κ-carrageenan (κ-Cg) doped with neodymium triflate (NdTrif3) and glycerol (Gly) were obtained by means of a simple, clean, fast, and low-cost procedure. The aim was to produce near-infrared (NIR)-emitting materials with improved thermal and mechanical properties, and enhanced ionic conductivity. Cg has a particular interest, due to the fact that it is a renewable, cost-effective natural polymer and has the ability of gelling in the presence of certain alkali- and alkaline-earth metal cations, being good candidates as host matrices for accommodating guest cations. The as-synthesised κ-Cg-based membranes are semi-crystalline, reveal essentially a homogeneous texture, and exhibit ionic conductivity values 1⁻2 orders of magnitude higher than those of the κ-Cg matrix. A maximum ionic conductivity was achieved for 50 wt.% Gly/κ-Cg and 20 wt.% NdTrif3/κ-Cg (1.03 × 10-4, 3.03 × 10-4, and 1.69 × 10-4 S cm-1 at 30, 60, and 97 °C, respectively). The NdTrif-based κ-Cg membranes are multi-wavelength emitters from the ultraviolet (UV)/visible to the NIR regions, due to the κ-Cg intrinsic emission and to Nd3+, 4F3/2→4I11/2-9/2.

Encapsulation of a [Dy(OH2)8](3+) cation: magneto-optical and theoretical studies of a caged, emissive SMM.

The first supramolecular cage formed by three benzo-15-crown-5 macrocycles encapsulating a [Dy(OH2)8](3+) guest cation is reported, with the Dy(iii) centre exhibiting local pseudo square antiprismatic D4d symmetry. The anisotropy barrier extracted from ac susceptibility studies, emission spectroscopy and ab initio calculations reveals that the second excited state Kramers doublet plays a key role in the magnetization dynamics due to the Ising character and near coparallel nature of the ground and first excited Kramers doublets.

Fabrication of low-cost thermo-optic variable wave plate based on waveguides patterned on di-ureasil hybrids.

An integrated variable wave plate device based on a thermo-optic (TO) effect was fabricated by patterning a waveguide channel through direct UV laser writing on the surface of sol-gel derived organic-inorganic hybrid (di-ureasil) films. The di-ureasil layer is stable up to 250 °C and has a high TO coefficient calculated as -(4.9 ± 0.5) × 10(-4) °C(-1) at 1550 nm. The waveguide temperature was tuned, inducing optical phase retardation between the transverse electric and transverse magnetic modes, resulting in a controllable wave plate. A maximum phase retardation of 77 ° was achieved for a waveguide induced temperature increase of 5 °C above room temperature, with a power consumption of 0.4 W. The thermal linear retardation coefficient was calculated to be 19 ± 1 °/ °C.

Luminescent DNA- and agar-based membranes.

Luminescent materials containing europium ions are investigated for different optical applications. They can be obtained using bio-macromolecules, which are promising alternatives to synthetic polymers based on the decreasing oil resources. This paper describes studies of the DNA- and Agar-europium triflate luminescent membranes and its potential technological applications are expanded to electroluminescent devices. Polarized optical microscopy demonstrated that the samples are birefringent with submicrometer anisotropy. The X-ray diffraction analysis revealed predominantly amorphous nature of the samples and the atomic force microscopy images showed a roughness of the membranes of 409.0 and 136.1 nm for the samples of DNA10Eu and Agar1.11Eu, respectively. The electron paramagnetic resonance spectra of the DNA(n)Eu membranes with the principal lines at g ≈ 2.0 and g ≈ 4.8 confirmed uniform distribution of rare earth ions in a disordered matrix. Moreover, these strong and narrow resonance lines for the samples of DNA(n)Eu when compared to the Agar(n)Eu suggested a presence of paramagnetic radicals arising from the DNA matrix. The emission spectra suggested that the Eu3+ ions occupy a single local environment in both matrices and the excitation spectra monitored around the Eu emission lines pointed out that the Eu3+ ions in the Agar host were mainly excited via the broad band component rather than by direct intra-4f(6) excitation, whereas the opposite case occurred for the DNA-based sample.

Highly emissive Zn-Ln metal-organic frameworks with an unusual 3D inorganic subnetwork.

Mixed zinc-lanthanide (Zn-Ln) metal-organic frameworks (MOFs) based on the 3,5-pyrazoledicarboxylate ligand exhibit an unusual three-dimensional (3D) inorganic subnetwork and display highly efficient photoluminescence.

Li(+)- and Eu(³+)-doped poly(ε-caprolactone)/siloxane biohybrid electrolytes for electrochromic devices.

The sol-gel process has been successfully combined with the "mixed cation" effect to produce novel luminescent and ion conducting biohybrids composed of a diurethane cross-linked poly(ε-caprolactone) (PCL530)/siloxane hybrid network (PCL stands for the poly(ε-caprolactone) biopolymer and 530 is the average molecular weight in gmol(-1)) doped with a wide range of concentrations of lithium and europium triflates (LiCF(3)SO(3) and Eu(CF(3)SO(3))(3), respectively) (molar ratio of ca. 50:50). The hybrid samples are all semicrystalline: whereas at n = 52.6 and 27.0 (n, composition, corresponds to the number of (C(═O)(CH(2))(5)O) repeat units of PCL(530) per mixture of Li(+) and Eu(3+) ions) a minor proportion of crystalline PCL(530) chains is present, at n = 6.1, a new crystalline phase emerges. The latter electrolyte is thermally stable up to 220 °C and exhibits the highest conductivity over the entire range of temperatures studied (3.7 × 10(-7) and 1.71 × 10(-4) S cm(-1) at 20 and 102 °C, respectively). According to infrared spectroscopic data, major modifications occur in terms of hydrogen bonding interactions at this composition. The electrochemical stability domain of the biohybrid sample with n = 27 spans more than 7 V versus Li/Li(+). This sample is a room temperature white light emitter. Its emission color can be easily tuned across the Commission Internationale d'Éclairage (CIE) chromaticity diagram upon simply changing the excitation wavelength. Preliminary tests performed with a prototype electrochromic device (ECD) comprising the sample with n = 6.1 as electrolyte and WO(3) as cathodically coloring layer are extremely encouraging. The device exhibits switching time around 50 s, an optical density change of 0.15, good open circuit memory under atmospheric conditions (ca. 1 month) and high coloration efficiency (577 cm(2) C(-1) in the second cycle).

Enhanced Eu3+ emission in aqueous phosphotungstate colloidal systems: stabilization of polyoxometalate nanostructures.

Luminescent Eu(3+)-containing polyphosphate-tungstate aqueous colloidal systems were prepared and studied as a function of the relative polyphosphate-tungstate content. In polyphosphate-rich solutions, Eu(3+) ions occupy cagelike sites composed of phosphate groups from the metaphosphate chains. In these sites, an average number of 0.5 water molecule coordinates to an Eu(3+) ion and the (5)D(0) emission quantum efficiency is 0.22. Tungstate addition leads to important modifications in neighboring Eu(3+) leading to coordination sites in the aqueous medium where metal ions are completely hidden from interactions with solvent molecules. Transmission electron microscopy results clearly show W-rich nanoparticles with sizes between 5 and 10 nm for all tungstate relative concentrations. For high tungstate relative contents (above 30 mol %), spectroscopic results suggest the presence of Eu(3+) in polyoxometalate (POM)-like sites by comparison with the well-known decatungstoeuropate [EuW(10)O(36)](9-) structure. These new aqueous colloids display surprisingly high (5)D(0) emission quantum efficiencies of ca 80% because of the strong ligand field provided by tungstate POM ligands and the complete absence of water molecules from the Eu(3+) first coordination shell.