Synthesis, characterization and molecular structures of the pyridinium trans-bis(pyridine)tetrachlororuthenate(III) and pyridinium trans-(carbonyl)(pyridine)tetrachlororuthenate(III)

The pyH[trans-RuCl4(py)2](1) and pyH[trans-RuCl4(CO)(py)](2) complexes were synthesized and found to crystallize in space group P21/n, Z = 4 with a = 8.080(7), b = 22.503(7), c = 10.125(6) Å, β = 93.19(6)° for (1) and a = 7.821(1), b = 10.337(3), c = 19.763(3) Å, β = 93.07(1)° for (2). The structures were solved by Patterson and difference Fourier techniques and refined to R = 0.062 for (1) and R = 0.038 for (2). In both cases the Ru(III) ion is octahedrally coordinated to four co-planar chlorine atoms, the nitrogen of the pyridine rings or carbon from the carbon monoxide. Another protonated pyridine group, which forms the counter-cation completes the crystal structures. The UV-Vis absorption spectra show three bands: (1) 360 (ε = 1180 M-1 cm-1), 441 (ε = 3200 M-1 cm-1) and 532 nm (ε = 400 M-1 cm-1); (2) 315(ε = 1150 M-1 cm-1), 442 (ε = 3170 M-1 cm-1) and 530 nm (ε = 390 M-1 cm-1). The two higher energy bands were associated with ligand-to-metal charge transfer transitions and a third band at lower energy was assigned to a d-d transition. Low temperature EPR data confirmed the presence of the paramagnetically active Ru(III) and it is consistent with axial symmetry of the complexes. The position of the stretching CO band in complex (2) is discussed in terms of metal-CO backbonding.

White light emission of Eu3+-based hybrid xerogels

The luminescence spectra and extended x-ray-absorption fine-structure (EXAFS) measurements of a series of Eu3+-based organic/inorganic xerogels were reported and related to the local coordination of the lanthanide cations. The hybrid matrix of these organically modified silicates, classed as U(2000) ureasils, is a siliceous network to which short organic chains containing oxyethylene units are covalently grafted by means of urea bridges. The luminescent centers were incorporated as europium triflate, Eu(CF3SO3)3, and europium bromide, EuBr3, with concentrations 200≥n≥20 and n=80, 40, and 30, respectively - where n is the number of ether oxygens in the polymer chains per Eu3+ cation. EXAFS measurements were carried out in some of the U(2000)nEu(CF3SO3)3 xerogels (n=200, 80, 60, and 40). The obtained coordination numbers N ranging from 12.8, n=200, to 9.7, n=40, whereas the average Eu3+ first neighbors distance R is 2.48-2.49 Å. The emission spectra of these multiwavelength phosphors superpose a broad green-blue band to a series of yellow-red narrow 5D0→7F0-4 Eu3+ lines and to the eye the hybrids appeared to be white, even at room temperature. The ability to tune the emission of the xerogels to colors across the chromaticity diagram is achieved by changing the excitation wavelength and the amount of salt incorporated in the hybrid host. The local environment of Eu3+ is described as a continuous distribution of closely similar low-symmetry network sites. The cations are coordinated by the carbonyl groups of the urea moieties, water molecules, and, for U(2000)nEu(CF3SO3)3, by the SO3 end groups of the triflate anions. No spectral evidences have been found for the coordination by the ether oxygens of the polyether chains. A mean radius for the first coordination shell of Eu3+ is calculated on the basis of the emission energy assignments. The results obtained for U(2000)nEu(CF3SO3)3, 2.4 Å for 90 ≥n≥40 and 2.6 and 2.5 Å for n=30 and 20, respectively, are in good agreement with the values calculated from EXAFS measurements. The energy of the intraconfigurational charge-transfer transitions, the redshift of the 5D0→7F0 line, with respect to the value calculated for gaseous Eu3+, and the hypersensitive ratio between the 5D0→7F2 and 5D0→7F1 transitions, point out a rather low covalency nature of the Eu3+ first coordination shell in these xerogels, comparing to the case of analogous polymer electrolytes modified by europium bromide. ©1999 The American Physical Society.

Fotocromismo e luminescência de compostos a base de tungstênio e íons terras raras trivalentes via síntese hidrotérmica

Pós-graduação em Química - IQ

Ultracold collisions between two light indistinguishable diatomic molecules: Elastic and rotational energy transfer in HD plus HD

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The energy landscape for solvent dynamics in electron transfer reactions: A minimalist model

Energy fluctuations of a solute molecule embedded in a polar solvent are investigated to depict the energy landscape for solvation dynamics. The system is modeled by a charged molecule surrounded by two layers of solvent dipolar molecules with simple rotational dynamics. Individual solvent molecules are treated as simple dipoles that can point toward or away from the central charge (Ising spins). Single-spin-flip Monte Carlo kinetics simulations are carried out in a two-dimensional lattice for different central charges, radii of outer shell, and temperatures. By analyzing the density of states as a function of energy and temperatures, we have determined the existence of multiple freezing transitions. Each of them can be associated with the freezing of a different layer of the solvent. (C) 2002 American Institute of Physics.

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Optical properties and energy transfer processes in (Tm3+, Nd3+) doped tungstate fluorophosphate glass

We investigate the linear optical properties and energy transfer processes in tungstate fluorophosphate glass doped with thulium (Tm3+) and neodymium (Nd3+) ions. The linear absorption spectra from 370 to 3000 nm were obtained. Transitions probabilities, radiative lifetimes, and transition branching ratios were determined using the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] theory. Frequency up-conversion to the blue region and fluorescence in the infrared were observed upon pulsed excitation in the range of 630-700 nm. The excitation spectra of the luminescence were obtained to understand the origin of the signals. The temporal decay of the fluorescence was measured for different concentrations of the doping ions. Energy transfer rates among the Tm3+ and Nd3+ ions were also determined.

Thermally enhanced cooperative energy-transfer frequency upconversion in terbium and ytterbium doped tellurite glass

Infrared-to-visible frequency upconversion through cooperative energy-transfer and thermal effects in Tb3+/Yb3+-codoped tellurite glasses excited at 1.064 mum is investigated. Bright luminescence emission around 485, 550, 590, 625 and 65 nm, identified as due to the D-5(4) --> F-7(J) (J= 6, 5, 4, 3, and 2) transitions of the terbium ions, respectively, was recorded. The excitation of the D-5(4) emitting level of the Tb3+ ions is assigned to cooperative energy-transfer from pairs of ytterbium ions.. The effect of temperature on the upconversion process was examined and the results revealed a fourfold upconversion enhancement in the 300-500 K interval. The enhancement of the upconversion process is due to the temperature dependence of the Yb3+-sensitizer absorption cross-section under anti-Stokes excitation. A rate-equation. model using multiphonon-assisted absorption for the ytterbium excitation combined with the energy migration effect between Yb-Yb pair, and Tb3+ ground-state depopulation via multiphonon excitation of the F-7(J) excited states describes quite well the experimental results. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Energy-transfer frequency upconversion in neodymium-sensitized praseodymium-doped PbGeO3-PbF2-CdF2 glass excited at 810 nm

Visible frequency upconversion emission through resonant energy-transfer involving neodymium and praseodymium ions in PbGeO3-PbF2-CdF2 glass excited by a semiconductor laser at 8 10 nm is investigated. Luminescence emission centered around 485, 530, 610, and 645 nm, which correspond to the P-3(0) -> H-3(4), P-3(1) + I-1(6) -> H-3(5), P-3(0) -> H-3(6) and P-1(0) -> F-3(2) transitions of praseodymium ions, respectively, are observed. The upconversion excitation of the Pr3+ ions excited-state emitting levels was accomplished by means of an ion-pair interaction involving ground-state absorption, multiphonon relaxation, and excited-state absorption of pump photons at 8 10 nm by the Nd3+ (I-4(9/2) -> H-2(9/2), F-4(5/2); F-4(3/2) -> P-2(1/2)) and direct energy-transfer to Pr3+ ((4)G(11/2) + K-2(11/2), H-3(4) -> I-4(9/2), P-3(1) + I-1(6)). The dependence of the upconversion emission intensity upon the excitation power, and neodymium concentration are also examined. (c) 2004 Elsevier B.V. All rights reserved.

Single molecule electron transfer dynamics in complex environments

We propose a new theoretical approach to study the kinetics of the electron transfer (ET) under the dynamical influence of the complex environments with the first passage times (FPT) of the reaction events. By measuring the mean and high order moments of FPT and their ratios, the full kinetics of ET, especially the dynamical transitions across different temperature zones, is revealed. The potential applications of the current results to single molecule electron transfer are discussed.

Energy transfer and frequency upconversion in Yb3+-Er3+-doped PbO-GeO2 glass containing silver nanoparticles

We report the infrared-to-visible frequency upconversion in Er3+-Yb3+-codoped PbO-GeO2 glass containing silver nanoparticles (NPs). The optical excitation is made with a laser at 980 nm in resonance with the F-2(5/2)-> F-2(7/2) transition of Yb3+ ions. Intense emission bands centered at 525, 550, and 662 nm were observed corresponding to Er3+ transitions. The simultaneous influence of the Yb3+-> Er3+ energy transfer and the contribution of the intensified local field effect due to the silver NPs give origin to the enhancement of the whole frequency upconversion spectra.

Smooth landscape solvent dynamics in electron transfer reactions

Solvent effects play a major role in controlling electron-transfer reactions. The solvent dynamics happens on a very high-dimensional surface, and this complex landscape is populated by a large number of minima. A critical problem is to understand the conditions under which the solvent dynamics can be represented by a single collective reaction coordinate. When this unidimensional representation is valid, one recovers the successful Marcus theory. In this study the approach used in a previous work [V. B. P. Leite and J. N. Onuchic; J. Phys. Chem. 100, 7680 (1996)] is extended to treat a more realistic solvent model, which includes energy correlation. The dynamics takes place in a smooth and well behaved landscape. The single shell of solvent molecules around a cavity is described by a two-dimensional system with periodic boundary conditions with nearest neighbor interaction. It is shown how the polarization-dependent effects can be inferred. The existence of phase transitions depends on a factor y proportional to the contribution from the two parameters of the model. For the present model, γ suggests the existence of weak kinetic phase transitions, which are used in the analysis of solvent effects in charge-transfer reactions. © 1999 American Institute of Physics.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Phonon-assisted cooperative energy transfer and frequency upconversion in a Yb3+/Tb3+ codoped fluoroindate glass

Phonon-assisted cooperative energy transfer and frequency upconversion (UC) in Yb3+/Tb3+ codoped fluoroindate glass were investigated. Anti-Stokes quasiresonant excitation of Yb3+ ions was used to study the influence of multiphonon transitions in the UC process. A rate equation model was used to describe the temperature dependence of the UC emission intensities and the theoretical results are in good agreement with the experimental data.

Dynamics of energy transfer and frequency upconversion in Tm3+ doped fluoroindate glass

The spectroscopic properties of Tm3+-doped fluoroindate glasses (FIG) were described by single wavelength pumping in the red region. The Judd-Ofelt (J-O) theory was used to obtain the quantum efficiency of the 4f-4f transitions and other spectroscopic parameters. The dynamics of the fluorescence was investigated and energy transfer (ET) processes among Tm3+ ions were studied. The results indicate that a two-step one-photon absorption process is responsible for the ultraviolet upconversion (UC) emissions, and dipole-dipole interaction provides the main contribution for ET rate is equal to the decay rate of noninteracting among active ions.