Extensive characterization of choline chloride and its solid-liquid equilibrium with water.

The importance of choline chloride (ChCl) is recognized due to its widespread use in the formulation of deep eutectic solvents. The controlled addition of water in deep eutectic solvents has been proposed to overcome some of the major drawbacks of these solvents, namely their high hygroscopicities and viscosities. Recently, aqueous solutions of ChCl at specific mole ratios have been presented as a novel, low viscous deep eutectic solvent. Nevertheless, these proposals are suggested without any information about the solid-liquid phase diagram of this system or the deviations from the thermodynamic ideality of its precursors. This work contributes significantly to this matter as the phase behavior of pure ChCl and (ChCl + H2O) binary mixtures was investigated by calorimetric and analytical techniques. The thermal behavior and stability of ChCl were studied by polarized light optical microscopy and differential scanning calorimetry, confirming the existence of a solid-solid transition at 352.2 ± 0.6 K. Additionally, heat capacity measurements of pure ChCl (covering both ChCl solid phases) and aqueous solutions of ChCl (xChCl < 0.4) were performed using a heat-flow differential scanning microcalorimeter or a high-precision heat capacity drop calorimeter, allowing the estimation of a heat capacity change of (ChCl) ≈ 39.3 ± 10 J K-1 mol-1, between the hypothetical liquid and the observed crystalline phase at 298.15 K. The solid-liquid phase diagram of the ChCl + water mixture was investigated in the whole concentration range by differential scanning calorimetry and the analytical shake-flask method. The phase diagram obtained for the mixture shows an eutectic temperature of 204 K, at a mole fraction of choline chloride close to xChCl = 0.2, and a shift of the solid-solid transition of ChCl-water mixtures of 10 K below the value observed for pure choline chloride, suggesting the appearance of a new crystalline structure of ChCl in the presence of water, as confirmed by X-ray diffraction. The liquid phase presents significant negative deviations to ideality for water while COSMO-RS predicts a near ideal behaviour for ChCl.

Photoluminescent materials based on silica doped with lanthanide complexes of 4'-formylbenzo-15-crown-5.

Photoluminescent materials were prepared by introducing lanthanide complexes of 4'-formylbenzo-15-crown-5 (C15H20O6) into a silica matrix obtained by the sol-gel method. The new lanthanide complexes [Ln(C15H20O6)(NO3)3(H2O)2] (Ln3+ = Sm3+, Eu3+ and Tb3+) were synthesized and were fully characterised using spectroscopic techniques, and elemental and thermogravimetric analysis. Photoluminescence measurements were performed for the isolated Eu3+ and Tb3+ complexes as well as for their related silica based materials. A detailed comparative analysis on the photoluminescent properties of the EU3+ complex and of its derived silica material was carried out.

Photoluminescent lanthanide-organic bilayer networks with 2,3-pyrazinedicarboxylate and oxalate.

The hydrothermal reaction between lanthanide nitrates and 2,3-pyrazinedicarboxylic acid led to a new series of two-dimensional (2D) lanthanide-organic frameworks: [Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)](n) [where 2,3-pzdc(2-) = 2,3-pyrazinedicarboxylate, ox(2-) = oxalate, and Ln(III) = Ce, Nd, Sm, Eu, Gd, Tb, or Er]. The structural details of these materials were determined by single-crystal X-ray diffraction (for Ce(3+) and Nd(3+)) that revealed the formation of a layered structure. Cationic monolayers of {(infinity)(2)[Ln(2,3-pzdc)(H(2)O)](+)} are interconnected via the ox(2-) ligand leading to the formation of neutral (infinity)(2)[Ln(2)(2,3-pzdc)(2)(ox)(H(2)O)(2)] bilayer networks; structural cohesion of the crystalline packing is reinforced by the presence of highly directional O-H...O hydrogen bonds between adjacent bilayers. Under the employed hydrothermal conditions 2,3-pyrazinedicarboxylic acid can be decomposed into ox(2-) and 2-pyrazinecarboxylate (2-pzc(-)), as unequivocally proved by the isolation of the discrete complex [Tb(2)(2-pzc)(4)(ox)(H(2)O)(6)].10H(2)O. Single-crystal X-ray diffraction of this latter complex revealed its co-crystallization with an unprecedented (H(2)O)(16) water cluster. Photoluminescence measurements were performed for the Nd(3+), Sm(3+), Eu(3+), and Tb(3+) compounds which show, under UV excitation at room temperature, the Ln(3+) characteristic intra-4f(N) emission peaks. The energy level of the triplet states of 2,3-pyrazinedicarboxylic acid (18939 cm(-1)) and oxalic acid (24570 cm(-1)) was determined from the 12 K emission spectrum of the Gd(3+) compound. The (5)D(0) and (5)D(4) lifetime values (0.333 +/- 0.006 and 0.577 +/- 0.017 ms) and the absolute emission quantum yields (0.13 +/- 0.01 and 0.05 +/- 0.01) were determined for the Eu(3+) and Tb(3+) compounds, respectively. For the Eu(3+) compound the energy transfer efficiency arising from the ligands' excited states was estimated (0.93 +/- 0.01).

Poly[[aqua-µ(3)-picolinato-µ(2)-picolinato-dipicolinatopotassium(I)terbium(III)] 2.5-hydrate].

In the title compound, [KTb(C(6)H(4)NO(2))(4)(H(2)O)]·2.5H(2)O, each Tb(3+) centre is coordinated by four N and five O atoms from five distinct picolinate ligands in a geometry resembling a highly distorted tricapped trigonal prism. One of the ligands establishes a skew bridge between neighbouring Tb(3+) centres, leading to the formation of one-dimensional anionic polymeric chains, {[(C(6)H(4)NO(2))(4)Tb](-)}(n), running along the direction [010]. Each K(+) cation is seven-coordinated by six O atoms from one anionic polymeric chain and one water mol-ecule [K⋯O 2.676 (3)-3.208 (4) Å]. The uncoordinated water mol-ecules are involved in O-H⋯O hydrogen bonding.

Photoluminescent, transparent and flexible di-ureasil hybrids containing CdSe/ZnS quantum dots.

We describe, in this paper, the sol-gel synthesis of di-ureasil based nanocomposites prepared in situ in the presence of organically capped CdSe quantum dots (QDs) or CdSe QDs which have been coated with a ZnS shell. For the latter a new chemical route to coat the CdSe QDs with ZnS shells was investigated and is now reported. The QDs became well dispersed in the final nanocomposites, whose microstructural homogeneity was evaluated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) analyses. In order to understand the optical behaviour of di-ureasil containing QDs, a detailed photoluminescent study was undertaken for a selected particle size distribution of ZnS coated CdSe QDs (d∼4.5 nm). Emission quantum yields up to 0.11 were measured in the final nanocomposites that present a huge (between 3 and 6 orders of magnitude) increase in the lifetime of the QDs (relative to that of isolated ones), as a result of energy transfer occurring between the intimately mixed di-ureasil host and the QDs.