Exploring Defect-Induced Emission in ZnAl2O4: An Exceptional Color-Tunable Phosphor Material with Diverse Lifetimes.

Activator-free zinc aluminate (ZA) nanophosphor was synthesized through a sol-gel combustion route, which can be used both as a blue-emitting phosphor material and a white-emitting phosphor material, depending on the annealing temperature during synthesis. The material also has the potential to be used in optical thermometry. These fascinating color-tunable emission characteristics can be linked with the various defect centers present inside the matrix and their changes upon thermal annealing. Various defect centers, such as anionic vacancy, cationic vacancy, antisite defect, etc., create different electronic states inside the band gap, which are responsible for the multicolor emission. The color components are isolated from the complex emission spectra using time-resolved emission spectroscopy (TRES) study. Interestingly, the lifetime values of the various defect centers were found to change significantly from milliseconds to microseconds upon thermal annealing, which makes the phosphors more diverse (i.e., either long-persistent blue-emitting phosphors or short-persistent white-emitting phosphors). Fourier transform infrared (FTIR) and diffuse reflectance spectroscopy (DRS) confirmed the presence of antisite defect centers such as AlZn+ or ZnAl- in the matrix. X-ray absorption fine structure (EXAFS) study showed that the spinel structure was more disordered in nature for low-temperature-annealed compounds. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) studies were also carried out in order to characterize various anionic and cationic vacancies and their clusters present in the compounds. Antisite defect centers such as AlZn+ or ZnAl-, which act as an electron or hole trap, were found to be responsible for the diverse lifetime behavior. To gain insight about the electronic states inside the band gap, density functional theory (DFT)-based calculations were performed for both pure and various vacancy-introduced spinel structures. Finally, based on the theoretical and experimental results, for the first time, a detailed investigation of various defect-induced emission behavior in ZA is presented, which also explains the mechanism of color tunability and dynamic lifetimes.

Deciphering the Role of Charge Compensator in Optical Properties of SrWO4:Eu3+:A (A = Li+, Na+, K+): Spectroscopic Insight Using Photoluminescence, Positron Annihilation, and X-ray Absorption.

Studies have been carried out to understand the specific role of the alkali charge compensator on the luminescence properties of an alkali ion (Li+, Na+, and K+) codoped SrWO4:Eu phosphor. The oxidation state of the europium ion was found to be +3 on the basis of X-ray absorption near edge structure (XANES) measurements. This is the first report of its kind where opposite effects of Li+ ion and Na+/K+ ions on photoluminescence intensity have been observed. Li+ ion codoping enhanced the photoluminescence intensity from SrWO4:Eu3+ phosphor while Na+/K+ ion codoping did not. On the other hand, the luminescence lifetime is maximum for the Na+ ion codoped sample and minimum for the Li+ ion codoped sample. The results could be explained successfully using time-resolved luminescence, positron annihilation lifetime spectroscopy (PALS), and extended X-ray absorption fine structure (EXAFS) spectroscopy measurements. Changes in the Eu-O bond length and Debye-Waller Factor (σ2) upon Li+/Na+/K+ codoping were monitored through EXAFS measurements. PALS also highlighted the fact that Li+ codoping is not contributing to reduction in the cation vacancies and might be occupying interstitial sites rather than lattice positions due to its very small size. On europium doping there is lowering in symmetry of SrO8 polyhedra from S4 to C6, which is reflected in an intense electric dipole transition in comparison to the magnetic dipole transition. This is also corroborated using trends in Judd-Ofelt parameters. The results have shown that the luminescence lifetime is better when the vacancy concentration is lower as induced by Na+ and K+ codoping, while the emission intensity is higher in the samples when distortion around Eu3+ is reduced as induced by Li+ codoping.

Subtle Structural Changes in (CuIIL)2MnII Complexes To Induce Heterometallic Cooperative Catalytic Oxidase Activities on Phenolic Substrates (H2L = Salen Type Unsymmetrical Schiff Base).

A new Cu(II) complex of an asymmetrically dicondensed Schiff base (H2L = N-(2-hydroxyacetophenylidene)-N'-salicylidene-1,3-propanediamine) derived from 1,3-propanediamine, salicylaldehyde, and o-hydroxyacetophenone has been synthesized. Using this complex, [CuL] (1), as a metalloligand, two new trinuclear Cu-Mn complexes, [(CuL)2Mn(N3)(H2O)](ClO4)·H2O (2) and [(CuL)2Mn(NCS)2] (3), have been prepared. Single-crystal structural analyses reveal that complexes 2 and 3 both have the same bent trinuclear {(CuL)2Mn}2+ structural unit in which two terminal bidentate square-planar (CuL) units are chelated to the central octahedral Mn(II) ion. This structural similarity is also evident from the variable-temperature magnetic susceptibility measurements, which suggest that compounds 2 and 3 are both antiferromagnetically coupled with comparable exchange coupling constants (-21.8 and -22.3 cm-1, respectively). The only difference between 2 and 3 lies in the coordination around the central Mn(II) ion; in 3, two SCN- groups are coordinated to the Mn(II), leaving a neutral complex, but in 2, one N3- group and one H2O molecule are coordinated to give a positively charged species. The presence of such a labile H2O coligand makes 2 catalytically active in mimicking two well-known polynuclear copper proteins, catecholase and phenoxazinone synthase. The turnover numbers (kcat) for the aerial oxidation of 3,5-di-tert-butylcatechol and o-aminophenol are 1118 and 6581 h-1, respectively, values which reflect the facility of the heterometallic catalyst in terms of both efficiency and catalytic promiscuity for aerial dioxygen activation. The mechanisms of these biomimetic oxidase reactions are proposed for the first time involving any heterometallic catalyst on the basis of mass spectral analysis, EPR spectroscopy, and cyclic voltammetry. The evidence of the intermediates indicates possible heterometallic cooperative activity where the substrates bind to a Mn(II) center and Cu(II) plays the role of an electron carrier for transformation of the phenolic substrates to their respective products with the reduction of aerial dioxygen.

Origin of Blue-Green Emission in α-Zn2P2O7 and Local Structure of Ln3+ Ion in α-Zn2P2O7:Ln3+ (Ln = Sm, Eu): Time-Resolved Photoluminescence, EXAFS, and DFT Measurements.

Considering the fact that pyrophosphate-based hosts are in high demand for making highly efficient luminescence materials, we doped two visible lanthanide ions, viz. Sm3+ and Eu3+, in Zn2P2O7. Interestingly, it was oberved that pure Zn2P2O7 displayed blue-green dual emission on irradiation with ultraviolet light. Emission and lifetime spectroscopy shows the presence of defects in pyrophosphate samples which are responsible for such emission. DFT calculations clearly pinpointed that the electronic transitions between defect states located at just below the conduction band minimum (arises due to VO1+ and VO2+ defects) and valence band maximum, as well as impurity states situated in the band gap, can lead to dual emission in the blue-green region, as is also indicated by emission and lifetime spectra. X-ray absorption near edge spectroscopy (XANES) shows the stabilization of europium as well as samarium ion in the +3 oxidation state in α-Zn2P2O7. The fact that α-Zn2P2O7 has two different coordination numbers for zinc ions, i.e. five- and six-coordinate, the study of dopant ion distribution in this particular matrix will be an important step in realizing a highly efficient europium- and samarium-based red-emitting phosphor. Time resolved photoluminescence (TRPL) shows that both of these ions are heterogeneously distributed between five- and six-coordinated Zn2+ sites and it is the six-coordinated Zn2+ site which is the most favorable for lanthanide ion doping. Extended X-ray absorption fine structure (EXAFS) measurements also suggested that a six-coordinated zinc ion is the preferred site occupied by trivalent lanthanide ions, which is in complete agreement with TRPL results. It was observed that there is almost complete transfer of photon energy from Zn2P2O7 to Eu3+, whereas this transfer is inefficient and almost incomplete in case of Sm3+, which is indeed important information for the realization of pyrophosphate-based tunable phosphors.

Luminescence Properties of SrZrO3/Tb(3+) Perovskite: Host-Dopant Energy-Transfer Dynamics and Local Structure of Tb(3+).

SrZrO3 perovskite (SZP) was synthesized using gel-combustion route and characterized systematically using X-ray diffraction and time-resolved photoluminescence techniques. A detailed analysis of the optical properties of Tb(3+) ions in SrZrO3 was performed to correlate them with the local environment of the lanthanide ions in this perovskite. Photoluminescence (PL) spectroscopy showed that emission spectrum consists of host as well as Tb(3+) emission indicating the absence of complete host-dopant energy transfer. On the basis of emission spectrum and PL decay study it was also observed that Tb(3+) is not homogeneously distributed in SrZrO3 perovskite; rather, it is occupying two different sites. It is corroborated using extended X-ray absorption fine structure studies that Tb(3+) is stabilized on both six-coordinated Zr(4+) and eight-coordinated Sr(2) site. The energies calculated using density functional theory (DFT) indicates that Tb occupation in Sr site is energetically more favorable than Zr site. The analysis of valence charge distribution also substantiated our structural stability analysis of site-selective Tb doping in SrZrO3. Time-resolved emission spectroscopy is employed to elucidate the difference in the spectral feature of Tb(3+) ion at Sr(2+) and Zr(4+) site. DFT-calculated density of states analysis showed that energy mismatch of Tb-d states with Zr-d and O-p states of SZP makes the energy transfer from host SZP to Tb(3+) ion difficult.

Differences in nuclearity, molecular shapes, and coordination modes of azide in the complexes of Cd(II) and Hg(II) with a "metalloligand" [CuL] (H2L = N,N'-bis(salicylidene)-1,3-propanediamine): characterization in solid and in solutions, and theoretical calculations.

Two new heterometallic copper(II)-mercury(II) complexes [(CuL)Hg(N3)2]n (1) and [(CuL)2Hg(N3)2] (2) and one copper(II)-cadmium(II) complex [(CuL)2Cd(N3)2] (3) have been synthesized using "metalloligand" [CuL] (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) and structurally characterized. Complex 1 is a one-dimensional (1D) helical coordination polymer constructed by the joining of the dinuclear [(CuL)Hg(N3)2] units through a single µ-l,l azido bridge. In the dinuclear unit the Hg(II) is bonded with two phenoxido oxygen atoms of "metalloligand" [CuL] and two nitrogen atoms of azido ligands. Complex 2 is a linear trinuclear entity, in which two terminal "metalloligands" [CuL] are coordinated to central Hg(II) through double phenoxido bridges. The azido ligands link the central mercury atom with the terminal copper atoms via µ-l,3 bridges. In contrast, the trinuclear complex 3 is bent. Here, in addition to two double phenoxido bridges, central Cd(II) is bonded to two mutually cis nitrogen atoms of two terminal azido ligands. The variation in the coordination modes of the azido ligand seems to be responsible for the different molecular shapes of 2 and 3. Interestingly, bond distances between the Hg atoms and the central nitrogen atom of the azido ligands are 2.790(4) and 2.816(5) Å in 1 and 2.823(4) Å in 2. These bond distances are significantly less than the sum of van der Waals radii of mercury (2.04 Å) and nitrogen (1.55 Å) and considerably longer than the sum of their covalent radii (2.03 Å). However the distances are similar to reported Hg-N bond distances of some Hg(II) complexes. Therefore, we have performed a theoretical density functional theory study to know whether there is any interaction between the central nitrogen atom of the azido ligand and the mercury atoms. We have used the Bader's "atoms-in-molecules", energetic and orbital analyses to conclude that such interaction does not exist. The probable reason for different molecular shapes observed in trinuclear complexes of 2 and 3 also has been studied and explained by theoretical calculations and using the CSD. Electronic spectra, EPR spectra and ESI mass spectra show that all three complexes lose their solid state identity in solution.

Synthesis of undoped and manganese-doped hgte nanoparticles using [Hg(TeCH2CH2NMe2)2] as a single source precursor.

The Reaction of [HgCl2(tmeda)] with NaTeCH2CH2NMe2 gave a mercury tellurolate, [Hg(TeCH2CH2. NMe2)2] (1) as a yellow crystalline solid, which was characterized by elemental analysis, UV-vis, mass and NMR (1H, 13C, 125Te, 199Hg) spectroscopy. Thermolysis of 1 in hexadecylamine (HDA) at 90 degrees C in the absence and presence of Mn(OAc)2.4H2O gave undoped and Mn-doped HgTe nanoparticles which were characterized by XRD, EDAX, TEM, EPR and magnetic measurements. These particles could be synthesized with mean particle size of 6-7 nm (from TEM). Manganese substitution at Hg site in HgTe lead to a linear decrease in lattice parameter with increasing concentration of Mn. Magnetization measurements showed ferromagnetic ordering at room temperature with very small coercive field (Hc, 50 Oe) for Hg0.973 Mn0.027 Te sample. This sample also exhibited distinct ferromagnetic resonance (FMR) in the EPR spectrum.

Comparative study of copper(II)-curcumin complexes as superoxide dismutase mimics and free radical scavengers.

Two stoichiometrically different copper(II) complexes of curcumin (stoichiometry, 1:1 and 1:2 for copper:curcumin), were examined for their superoxide dismutase (SOD) activity, free radical-scavenging ability and antioxidant potential. Both the complexes are soluble in lipids and DMSO. The formation constants of the complexes were determined by voltammetry. EPR spectra of the complexes in DMSO at 77K showed that the 1:2 Cu(II)-curcumin complex is square planar and the 1:1 Cu(II)-curcumin complex is distorted orthorhombic. Cu(II)-curcumin complex (1:1) with larger distortion from square planar structure shows higher SOD activity. These complexes inhibit gamma-radiation induced lipid peroxidation in liposomes and react with DPPH acting as free radical scavengers. One-electron oxidation of the two complexes by radiolytically generated azide radicals in Tx-100 micellar solutions produced phenoxyl radicals, indicating that the phenolic moiety of curcumin in the complexes participates in free radical reactions. Depending on the structure, these two complexes possess different SOD activities, free radical neutralizing abilities and antioxidant potentials. In addition, quantum chemical calculations with density functional theory have been performed to support the experimental observations.

The first examples of multiply bonded dirhenium(iii,ii) paramagnetic complexes containing nitrobenzoate ligands: spectroscopic, structural, cytotoxicity and computational studies.

4-Nitrobenzoic acid, 3-nitrobenzoic acid and 4'-nitro[1,1'-biphenyl]-4-carboxylic acid react with the multiply bonded paramagnetic dirhenium(iii,ii) complex Re2(µ-O2CCH3)Cl4(µ-Ph2PCH2PPh2)2 (1) in refluxing ethanol to afford the paramagnetic substitution products of the type Re2(µ-L)Cl4(µ-Ph2PCH2PPh2)2, where L represents the nitrobenzoate ligands [L = 4-nitrobenzoate, 2; 3-nitrobenzoate, 3; 4'-nitro[1,1'-biphenyl]-4-carboxylate, 4]. These are the first examples of paramagnetic dirhenium complexes containing nitrobenzoate ligands. The spectral (UV-vis, IR, and EPR) and electrochemical properties of the complexes are described. The identity of 4 has been established by single-crystal X-ray structure determination (Re-Re distance of 2.2967(4) Å). The electronic structures of the complexes were scrutinized by density functional theory (DFT) calculations. X-band EPR spectral measurements along with the DFT analysis show that the unpaired electron resides in the metal-metal δ* antibonding orbital. The complexes were also screened in vitro for their antiproliferative properties against the human breast cancer cell line MCF-7 by the MTT assay. Flow cytometry analysis showed that the complexes arrested the sub-G0/G1 phase.

Investigations on local structures in new Bi2-2xLa2xUO6 (x = 0-0.05) solid solutions: a combined XRD, EXAFS, PL and EPR study.

La doped Bi2UO6 solid solutions of the general formula Bi2-2xLa2xUO6 (x = 0-0.05) were prepared by the solid state reaction of Bi2O3, La(OH)3 and U3O8 in a stoichiometric ratio. These solid solutions were characterized by X-ray diffraction, Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Spectroscopy (XANES) studies. It was found that La goes to the Bi sites of the Bi2UO6 lattice during the formation of these solid solutions. For further confirmation, a photoluminescence (PL) study on an iso-structural Bi1.96Eu0.04UO6 was performed, and this supports the above observation. The solid solutions were also probed by EPR studies. The PL and EPR studies suggest that there are doping induced oxygen vacancies in these solid solutions.

Unprecedented structural variations in trinuclear mixed valence Co(II/III) complexes: theoretical studies, pnicogen bonding interactions and catecholase-like activities.

Three new mixed valence trinuclear Co(II/III) compounds cis-[Co3L2(MeOH)2(N3)2(µ1,1-N3)2] (1), trans-[Co3L2(H2O)2(N3)2(µ1,1-N3)2]·(H2O)2 (2) and [Co3L(R)2(N3)3(µ1,3-N3)] (3) have been synthesized by reacting a di-Schiff base ligand (H2L) or its reduced form [H2LR] (where H2L= N,N'-bis(salicylidene)-1,3-propanediamine and H2LR= N,N'-bis(2-hydroxybenzyl)-1,3-propanediamine) with cobalt perchlorate hexahydrate and sodium azide. All three products have been characterized by IR, UV-Vis and EPR spectroscopies, ESI-MS, elemental, powder and single crystal X-ray diffraction analyses. Complex 2 is an angular trinuclear species in which two terminal octahedral Co(III)N2O4 centers coordinate to the central octahedral cobalt(II) ion through µ2-phenoxido oxygen and µ1,1-azido nitrogen atoms along with two mutually cis-oxygen atoms of methanol molecules. On the other hand, in linear trinuclear complex , in addition to the µ2-phenoxido and µ1,1-azido bridges with terminal octahedral Co(III) centres, the central Co(II) is bonded with two mutually trans-oxygen atoms of water molecules. Thus the cis-trans configuration of the central Co(II) is solvent dependent. In complex 3, the two terminal octahedral Co(III)N2O4 centers coordinate to the central penta-coordinated Co(II) ion through double phenoxido bridges along with the nitrogen atom of a terminal azido ligand. In addition, the two terminal Co(III) are connected through a µ1,3-azido bridge that participates in pnicogen bonding interactions (intermolecular N-N interaction) as an acceptor. Both the cis and trans isomeric forms of 1 and 2 have been optimized using density functional theory (DFT) calculations and it is found that the cis configuration is energetically more favorable than the trans one. However, the trans configuration of 2 is stabilized by the hydrogen bonding network involving a water dimer. The pnicogen bonding interactions have been demonstrated using MEP surfaces and CSD search which support the counter intuitive electron acceptor ability of the µ1,3-azido ligand. Complexes 1-3 exhibit catecholase-like activities in the aerial oxidation of 3,5-di-tert-butylcatechol to the corresponding o-quinone. Kinetic data analyses of this oxidation reaction in acetonitrile reveal that the catecholase-like activity follows the order: 1 (kcat = 142 h(-1)) > 3 (kcat = 99 h(-1)) > 2 (kcat = 85 h(-1)). Mechanistic investigations of the catalytic behaviors by X-band EPR spectroscopy and estimation of hydrogen peroxide formation indicate that the oxidation reaction proceeds through the reduction of Co(III) to Co(II).

Interaction of metal ions with D-glucobenzothiazoline: isolation and characterization of the resultant products.

Six different metal-ion complexes of D-glucobenzothiazoline were synthesized and characterized by analytical and spectral techniques. Formation of different types of species (ML and ML(2)) were observed with Cu(2+), Ag(+), Cd(2+), Hg(2+), and Zn(2+) ions. Existence of an anomeric mixture in the case of the Cu(2+) complex is identified from the EPR spectra, and the results were further supported by the simulated spectra. The structures were proposed based on different studies.

Molecular magnetic properties of two-copper(II) containing complexes [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2. An EPR study.

Electron paramagnetic resonance (EPR) investigations were conducted on [Cu(II) (1-phenylamidino-O-n-butylurea) en (H2O)]2(2+) (1) and [Cu(II) sulphato-mono (1-phenylamidino-O-methylurea)]2 (2) respectively, in the temperature range 300-77K. Fine structure characteristics of S = 1 system, was observed in both complexes with zero field splitting of 0.0525 and 0.0225 cm(-1), respectively, suggesting the formation of dimeric complexes. The presence of the half-field signal (DeltaMs= +/-2), in the complex 1, further confirmed the formation of dimer. The temperature dependence of EPR signal intensity has given evidence for the ferromagnetic (FM) coupling between the two Cu2+ ions. The isotropic exchange interaction constants J, were evaluated from this and were found out to be approximately 57 and approximately 27 cm(-1), respectively, for the complexes 1 and 2. The photoacoustic spectra of these complexes had shown a band around 26,400 cm(-1) characteristic of metal-metal bonding giving an independent support for the existence of dimeric Cu2+ species. The high magnetic moment values at room temperature for complex 1 (2.68 microB) and complex 2 (2.00 microB), obtained from the magnetic susceptibility measurements, support the formation of ferromagnetically coupled Cu2+ dimers.