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This research delves into the influence of red lead content on the red and NIR emission characteristics of Pr3+ ions within a nonconventional antimony silicate glass system. The glasses were synthesized across a composition spectrum of (40 − x) Pb3O4‒49Sb2O3‒(10 + x)SiO2:1Pr2O3, where x ranged from 0 to 35 mol%. Characterization was carried out using XRD, DSC, XPS, and IR spectroscopy. These analyses unveiled the presence of antimony ions in both Sb3+ and Sb5+ states and lead ions in Pb4+ and Pb2+ states within these glass compositions. Optical absorption and emission spectra (at λexc = 445 nm) were recorded within the wavelength range of 400‒1800 nm. Luminescence decay profiles of two pivotal transitions, namely, 3P0 → 3F2 (red emission) and 1G4 → 3H5 (1.3 µm NIR emission), were also recorded. Various radiative parameters from these spectra were extracted using the J–O theory. The findings indicated that, as the Pb3O4 content declined from 40 to 10 mol%, the covalent nature of the samples diminished, resulting in a remarkable amplification in the intensity of both the red and NIR emission bands of Pr3+ ions. The glass containing 10 mol% of Pb3O4 exhibited the most elevated radiative parameters and quantum efficiency. This augmentation was attributed to the reduction of Pb4+ and Sb5+ ions within the glass network or the augmentation of Pb2+ ions, serving as modifiers that mitigated phonon losses. Consequently, glasses with 10 mol% Pb3O4 demonstrate great potential for telecommunications applications, owing to their significant enhancement in PL emission for the 3P0 → 3F2 and 1G4 → 3H5 transitions. [ABSTRACT FROM AUTHOR]

Abstract: PbO–As2O3 glasses mixed with different concentrations of Fe2O3 (ranging from 0 to 2.0mol%) were crystallized. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) techniques. Studies were extended to optical absorption, IR, ESR and magnetic susceptibility on these glass ceramic samples. The X-ray diffraction and scanning electron microscopic studies reveal the presence of PbFe4(As5O11)2, Fe2PbAs2O6 crystal phases. The optical absorption studies together with ESR and magnetic susceptibility measurements indicated the dominant presence of iron ions in the trivalent state when the concentration of nucleating agent Fe2O3 is less than 0.3mol%. The analysis of the IR spectra indicated a gradual transformation of iron ions from tetrahedral sites to octahedral sites as the concentration of Fe2O3 is increased beyond 0.3mol%. [Copyright &y& Elsevier]

Abstract: Li2O–CaF2–P2O5 glasses mixed with different concentrations of TiO2 (ranging from 0 to 0.8mol%) were crystallized at 500°C. The samples are characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. Spectroscopic properties (IR and Raman) and elastic properties (viz., Young''s modulus E, shear modulus G and micro-hardness H) at room temperature are studied. The X-ray diffraction and the scanning electron microscopic studies revealed the presence of lithium phosphate, lithium titanium phosphate and titanium phosphate crystal phases. The differential thermal analysis traces of these samples exhibit three crystalline temperatures. The IR and Raman spectra of these samples have exhibited bands due to TiO4 and TiO6 structural units in addition to the conventional bands due to various phosphate structural groups. The analysis of these results indicated that the sample crystallized with 0.6mol% of TiO2 possesses the highest density, high mechanical strength and more compact network. [Copyright &y& Elsevier]

Abstract: The results of various physical properties namely, dielectric properties (dielectric constant, loss tan δ, ac conductivity σ, over a wide range of frequency and temperature and dielectric breakdown strength in air medium at room temperature), optical absorption, electron spin resonance (ESR) at liquid nitrogen temperature and magnetic susceptibility at room temperature of Li2O–CaF2–P2O5:TiO2 glass-ceramics have been reported. The optical absorption and magnetic susceptibility studies indicated that the titanium ions exist in Ti3+ state in addition to Ti4+ state in these samples. However, the reduction seems to be the lowest in the sample containing 0.6mol% of TiO2. The dielectric constant and loss variation with the concentration of TiO2 have been explained on the basis of space charge polarization mechanism. The dielectric relaxation effects exhibited by these samples have been analyzed by a pseudo Cole–Cole plot method and the spreading of dielectric relaxation has been observed. The ac conductivity in the high temperature region seems to be related both with electronic and ionic movements. The low temperature (or the nearly temperature independent) part of conductivity could be explained on the basis of quantum mechanical tunneling model. The studies on dielectric breakdown strength indicated the highest insulating strength for the sample containing 0.6mol% of TiO2. [Copyright &y& Elsevier]

A new metal-organic framework compound, poly[[μ 7 -dihydrogen (4,5-di-cyano-1,2-phenyl-ene)diphospho-nato]-(oxonium)caesium], [Cs(C 8 H 4 N 2 O 6 P 2 )(H 3 O)] n (I), based on Cs + and the organic linker 4,5-di-cyano-1,2-phenyl-ene)bis-(phospho-nic acid, (H 4 cpp), containing two distinct coordinating functional groups, has been prepared by a simple diffusion method and its crystal structure is reported. The coordination polymeric structure is based on a CsO 8 N 2 complex unit comprising a monodentate hydro-nium cation, seven O-atom donors from two phospho-nium groups of the (H 2 cpp) 2- ligand, and two N-atom donors from bridging cyano groups. The high level of connectivity from both the metal cation and the organic linker allow the formation of a compact and dense three-dimensional network without any crystallization solvent. Topologically (I) is a seven-connected uninodal network with an overall Schäfli symbol of {4 17 .6 4 }. Metal cations form an undulating inorganic layer, which is linked by strong and highly directional O-H⋯O hydrogen-bonding inter-actions. These metallic layers are, in turn, connected by the organic ligands along the [010] direction to form the overall three-dimensional framework structure.

The preparation of coordination polymers (CPs) based on either transition metal centres or rare-earth cations has grown considerably in recent decades. The different coordination chemistry of these metals allied to the use of a large variety of organic linkers has led to an amazing structural diversity. Most of these compounds are based on carboxylic acids or nitrogen-containing ligands. More recently, a wide range of molecules containing phosphonic acid groups have been reported. For the particular case of Ca(2+)-based CPs, some interesting functional materials have been reported. A novel one-dimensional Ca(2+)-based coordination polymer with a new organic linker, namely poly[[diaqua[μ4-(4,5-dicyano-1,2-phenylene)bis(phosphonato)][μ3-(4,5-dicyano-1,2-phenylene)bis(phosphonato)]dicalcium(II)] tetrahydrate], {[Ca2(C8H4N2O6P2)2(H2O)2]·4H2O}n, has been prepared at ambient temperature. The crystal structure features one-dimensional ladder-like ∞(1)[Ca2(H2cpp)2(H2O)2] polymers [H2cpp is (4,5-dicyano-1,2-phenylene)bis(phosphonate)], which are created by two distinct coordination modes of the anionic H2cpp(2-) cyanophosphonate organic linkers: while one molecule is only bound to Ca(2+) cations via the phosphonate groups, the other establishes an extra single connection via a cyano group. Ladders close pack with water molecules through an extensive network of strong and highly directional O-H...O and O-H...N hydrogen bonds; the observed donor-acceptor distances range from 2.499 (5) to 3.004 (6) Å and the interaction angles were found in the range 135-178°. One water molecule was found to be disordered over three distinct crystallographic positions. A detailed solution-state NMR study of the organic linker is also provided.