Synthesis and spectroscopic behavior of highly luminescent Eu(3+)-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM)3L2] complexes (RE=Gd and Eu) with a variety of sulfoxide ligands; L=benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu(3+)-beta-diketonate complexes show characteristics narrow bands arising from the 5D0-->7F(J) (J=0-4) transitions, which are split according to the selection rule for C(n), C(nv) or C(s) site symmetries. The experimental Judd-Ofelt intensity parameters (Omega2 and Omega4), radiative (A(rad)) and non-radiative (A(nrad)) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Omega2 (61.9x10(-20)cm2) was obtained to the complex with PTSO ligand, indicating that Eu3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield (q) and emission quantum efficiency of the emitter 5D0 level (eta) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield (q=1%), for the hydrated complex [Eu(DBM)3H2O], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by (x, y) color coordinates.     

Biolabeling with nanoparticles based on Y2O3: Nd and luminescence detection in the near-infrared

Neodymium based fluorescence presents several advantages in comparison to conventional rare earth or enzyme-substrate based fluorescence emitting sources (e.g.Tb, HRP) . Based on this fact we have herein explored a Nd-based fluoroimmunoassay. We efficiently detected the presence of an oxidized low-density lipoprotein (oxLDL) in human plasma a well-known marker for cardiovascular diseases, which causes around 30% of deaths worldwide. Conventional fluoroimmunoassay uses time-resolved luminescence techniques, with detection in the visible range, to eliminate the fluorescence background from the biological specimens. By using an immunoassay based on functionalized Y₂O₃:Nd³⁺ nanoparticles, where the excitation and emission processes in the Nd³⁺ ion occur in the near-infrared (NIR) region, we have succeeded in eliminating the interferences from the biological fluorescence background, avoiding the use of time-resolved techniques. This yields higher emission intensity from the Nd³⁺-nanolabels and efficient detection of anti-oxidized low-density lipoproteins (anti-oxLDL) by Y₂O₃:Nd³⁺-antibody-antigen conjugation, leading to a novel biolabeling method.     

Enhancement of electromagnetically induced transparency in room temperature alkali metal vapor

Electromagnetically induced transparency (EIT) has led to several quantum optics effects such as lasing without inversion or squeezed light generation. More recently quantum memories based on EIT have been experimentally implemented in different systems such as alkali metal atoms. In this system the excited state of the optical transition splits into several sublevels due to the hyperfine interaction. However, most of the theoretical models used to describe the experimental results are based on a Λ-system with only one excited state. In this article, we present a theoretical model for the Λ-type interaction of two light, fields and an atomic system with multiple excited state. In particular we show that if the control and probe fields are orthogonally circularly polarized the EIT effect in an alkali-metal vapor can almost disappears. We also identify the reasons of this reduction and propose a method to recover the transparency via velocity selective optical pumping.     

Direct measurement of decoherence for entanglement between a photon and stored atomic excitation

Violations of a Bell inequality are reported for an experiment where one of two entangled qubits is stored in a collective atomic memory for a user-defined time delay. The atomic qubit is found to preserve the violation of a Bell inequality for storage times up to 21 micros, 700 times longer than the duration of the excitation pulse that creates the entanglement. To address the question of the security of entanglement-based cryptography implemented with this system, an investigation of the Bell violation as a function of the cross correlation between the generated nonclassical fields is reported, with saturation of the violation close to the maximum value allowed by quantum mechanics.     

Photoluminescent behavior of SrB4O7:RE (RE=Sm and Eu) prepared by Pechini, combustion and ceramic methods

This work reports the preparation of system containing RE²⁺ ions (RE=Sm and Eu)-doped in SrB₄O₇ matrix by ceramic, Pechini and combustion methods. These compounds were prepared by reduction of RE³⁺ to RE²⁺ in air, which exhibit some different features according to the preparation method. Photoluminescent properties of these systems were investigated based on the emission and excitation spectral data. The emission spectra of SrB₄O₇:Eu²⁺ system prepared by combustion and Pechini methods are characterized by a broad band assigned to interconfigurational 4f⁶5d→4f⁷ transition, while SrB₄O₇:Sm²⁺ compound exhibit narrow emission bands arising from intraconfigurational-4f⁶ also shows ⁴G_5/2→⁶H_J′ transitions ( and ) arising from Sm³⁺ ion, transitions. SrB₄O₇:RE system prepared by combustion method presents emission bands from RE³⁺ ions as intense as that arising from RE²⁺, suggesting that the preparation route is not efficient for the reduction RE³⁺→RE²⁺ process. Emission quantum efficiency and radiative emission rates of Sm²⁺ ion are determined and discussed.     

Synthesis and luminescent properties of Eu-complexes with 2-acyl-1,3-indandionates (ACIND) and TPPO ligands: The first X-ray structure of Eu–ACIND complex

Europium complexes presenting general formulas [Eu(ACIND)₃(H₂O)₂] and [Eu(ACIND)₃(TPPO)₂] have been synthesized and characterized. In these formulas ACIND is stands for the ligands 2-acetyl-1,3-indandionate (AIND), 2-isovaleryl-1,3-indandionate (ISOVIND) or 2-benzyl-1,3-indandionate (BIND). The [Eu(ISOVIND)₃(H₂O)(EtOH)] complex was also prepared and its structure determined by single crystal X-ray analysis, showing that this complex crystallize in a monoclinic space group P2₁/n with the water molecules bridging through the hydrogen bond. The Eu(III) ion is eight-coordinate in a bicapped trigonal prismatic geometry defined by the oxygen donor atoms with a site of symmetry close to C_2ν. Isovaleryl groups in the ISOVIND molecules in the structure are disordered over two positions of the europium complex. Carbon atoms in ethanol molecule are disordered by the thermal vibration. Photoluminescence properties of these complexes in solid state were investigated both experimentally and theoretically, suggesting an efficient ligand-to-metal intramolecular energy transfer process.     

Laser-noise-induced correlations and anti-correlations in electromagnetically induced transparency

High degrees of intensity correlation between two independent lasers were observed after propagation through a rubidium vapor cell in which they generate Electromagnetically Induced Transparency (EIT). As the optical field intensities are increased, the correlation changes sign (becoming anti-correlation). The experiment was performed in a room temperature rubidium cell, using two diode lasers tuned to the ⁸⁵Rb D₂ line (λ= 780 nm). The cross-correlation spectral function for the pump and probe fields is numerically obtained by modeling the temporal dynamics of both field phases as diffusing processes. We explored the dependence of the atomic response on the atom-field Rabi frequencies, optical detuning and Doppler width. The results show that resonant phase-noise to amplitude-noise conversion is at the origin of the observed signal and the change in sign for the correlation coefficient can be explained as a consequence of the competition between EIT and Raman resonance processes.     

Evaluation of intramolecular energy transfer process in the lanthanide(III) bis- and tris-(TTA) complexes: Photoluminescent and triboluminescent behavior

This work reports the energy transfer mechanism process of [Eu(TTA)₂(NO₃)(TPPO)₂] (bis-TTA complex) and [Eu(TTA)₃(TPPO)₂] (tris-TTA complex) based on experimental and theoretical spectroscopic properties, where TTA=2-thienoyltrifluoroacetone and TPPO=triphenylphosphine oxide. These complexes were synthesized and characterized by elemental analyses, infrared spectroscopy and thermogravimetric analysis. The theoretical complexes geometry data by using Sparkle model for the calculation of lanthanide complexes (SMLC) is in agreement with the crystalline structure determined by single-crystal X-ray diffraction analysis. The emission spectra for [Gd(TTA)₃(TPPO)₂] and [Gd(TTA)₂(NO₃)(TPPO)₂] complexes are associated to T→S₀ transitions centered on coordinated TTA ligands. Experimental luminescent properties of the bis-TTA complex have been quantified through emission intensity parameters Ω_λ (λ=2 and 4), spontaneous emission rates (A_rad), luminescence lifetime (τ), emission quantum efficiency (η) and emission quantum yield (q), which were compared with those for tris-TTA complex. The experimental data showed that the intensity parameter value for bis-TTA complex is twice smaller than the one for tris-TTA complex, indicating the less polarizable chemical environment in the system containing nitrate ion. A good agreement between the theoretical and experimental quantum yields for both Eu(III) complexes was obtained. The triboluminescence (TL) of the [Eu(TTA)₂(NO₃)(TPPO)₂] complexes are discussed in terms of ligand-to-metal energy transfer.     

Microwave-Assisted Preparation of Luminescent Inorganic Materials: A Fast Route to Light Conversion and Storage Phosphors

Luminescent inorganic materials are used in several technological applications such as light-emitting displays, white LEDs for illumination, bioimaging, and photodynamic therapy. Usually, inorganic phosphors (e.g., complex oxides, silicates) need high temperatures and, in some cases, specific atmospheres to be formed or to obtain a homogeneous composition. Low ionic diffusion and high melting points of the precursors lead to long processing times in these solid-state syntheses with a cost in energy consumption when conventional heating methods are applied. Microwave-assisted synthesis relies on selective, volumetric heating attributed to the electromagnetic radiation interaction with the matter. The microwave heating allows for rapid heating rates and small temperature gradients yielding homogeneous, well-formed materials swiftly. Luminescent inorganic materials can benefit significantly from the microwave-assisted synthesis for high homogeneity, diverse morphology, and rapid screening of different compositions. The rapid screening allows for fast material investigation, whereas the benefits of enhanced homogeneity include improvement in the optical properties such as quantum yields and storage capacity.     

Synthesis, characterization and spectroscopic investigation of new tetrakis(acetylacetonato)thulate(III) complexes containing alkaline metals as countercations

In this work a series of tetrakis complexes C[Tm(acac)₄], where C⁺=Li⁺, Na⁺ and K⁺ countercations and acac=acetylacetonate ligand, were synthesized and characterized for photoluminescence investigation. The relevant aspect is that these complexes are water-free in the first coordination sphere. The emission spectra of the tetrakis Tm³⁺-complexes present narrow bands characteristic of the ¹G₄→³H₆ (479 nm), ¹G₄→³F₄ (650 nm) and ¹G₄→³H₅ (779 nm) transitions of the Tm³⁺ ion, with the blue emission color at 479 nm as the most prominent one. The lifetime values (τ) of the emitting ¹G₄ level of the C[Tm(acac)₄] complexes were 344, 360 and 400 ns for the Li⁺, Na⁺ and K⁺ countercations, respectively, showing an increasing linear behavior versus the ionic radius of the alkaline ion. An efficient intramolecular energy transfer process from the triplet state (T) of the ligands to the emitting ¹G₄ state of the Tm³⁺ ion is observed. This fact, together with the absence of water molecules in first coordination sphere, allows these tetrakis Tm³⁺-complexes to act as efficient blue light conversion molecular devices.