Reversible Water Intercalation Accompanied by Coordination and Color Changes in a Layered Metal-Organic Framework

A new two-dimensional 3d-4f mixed-metal mixed dicarboxylate (homocyclic and heterocyclic) of the formula [Gd2(H2O)2Ni(H2O)2(1,2-bdc)2(2,5-pydc)2] 3 8H2O (1; 1,2-H2bdc = 1,2-benzenedicarboxylic acid and 2,5-H2pydc = 2,5- pyridinedicarboxylic acid) has been prepared by employing the hydrothermal method. The structure has infinite onedimensional-Gd-O-Gd- chains formed by the edge-shared GdO9 polyhedral units, resulting exclusively from the connectivity between the Gd3+ ions and the 1,2-bdc units. The chains are connected by the [Ni(H2O)2(2,5-pydc)2]2- metalloligand, forming the two-dimensional layer arrangements. The stacking of the layers creates hydrophilic and hydrophobic spaces in the interlamellar region. A one-dimensional water ladder structure, formed by the extraframework water molecules, occupies the hydrophilic region while the benzene ring of 1,2-bdc occupies the hydrophobic region. To the best of our knowledge, the present compound represents the first example of a 3d-4f mixed-metal carboxylate in which two different aromatic dicarboxylate anions act as the linkers. The stabilization energies of the water clusters have been evaluated using density functional theory calculations. The water molecules in 1 are fully reversible accompanied by a change in color (greenish blue to brown) and coordination around Ni2+ ions (octahedral to distorted tetrahedral).

Unusual Salt-Induced Color Modulation through Aggregation-Induced Emission Switching of a Bis-cationic Phenylenedivinylene-Based pi Hydrogelator

The synthesis, hydrogelation, and aggregation-induced emission switching of the phenylenedivinylene bis-N-octyl pyridinium salt is described. Hydrogelation occurs as a consequence of pi-stacking, van der Waals, and electrostatic interactions that lead to a high gel melting temperature and significant mechanical properties at a very low weight percentage of the gelator. A morphology transition from fiber-to-coil-to-tube was observed depending on the concentration of the gelator. Variation in the added salt type, salt concentrations, or temperature profoundly influenced the order of aggregation of the gelator molecules in aqueous solution. Formation of a novel chromophore assembly in this way leads to an aggregation-induced switch of the emission colors. The emission color switches from sky blue to white to orange depending upon the extent of aggregation through mere addition of external inorganic salts. Remarkably, the salt effect on the assembly of such cationic phenylenedivinylenes in water follow the behavior predicted from the well-known Hofmeister effects. Mechanistic insights for these aggregation processes were obtained through the counterion exchange studies. The aggregation-induced emission switching that leads to a room-temperature white-light emission from a single chromophore in a single solvent (water) is highly promising for optoelectronic applications.

Fluoranthene-Based Molecules as Electron Transport and Blue Fluorescent Materials for Organic Light-Emitting Diodes

Herein we report the synthesis, characterization, and potential application of his (4- (7,9,10-triphenylfluoranthen-8-yl)pheny)sulfone (TPFDPSO2) and 2,8-bis (7,9,10-triphenylfluoranthen-8-yl) dibenzo b, d]-thiophene 5,5-dioxide (TPFDBTO2) as electron transport as well as light-emitting materials. These fluoranthene derivatives were synthesized by oxidation of their corresponding parent sulfide compounds, which were prepared via Diels-Alder reaction. These materials exhibit deep blue fluorescence emission in both solution and thin film, high photoluminescence quantum yield (PLQY), thermal and electrochemical stability over a wide potential range. Hole- and electron-only devices were fabricated to study the charge transport characteristics, and predominant electron transport property comparable with that of a well-known electron transport material, Alq(3), was observed. Furthermore, bilayer electroluminescent devices were fabricated utilizing these fluoranthene derivatives as electron transport as well as emitting layer, and device performance was compared with that of their parent sulfide molecules. The electroluminescence (EL) devices fabricated with these molecules displayed bright sky blue color emission and 5-fold improvement in external quantum efficiency (EQE) with respect to their parent compounds.

I. Phosphorescence and the true lifetime of triplet states in fluid solutions. II. Why is condensed oxygen blue?

I. PHOSPHORESCENCE AND THE TRUE LIFETIME OF TRIPLET STATES IN FLUID SOLUTIONS

Phosphorescence has been observed in a highly purified fluid solution of naphthalene in 3-methylpentane (3-MP). The phosphorescence lifetime of C₁₀H₈ in 3-MP at -45 °C was found to be 0.49 ± 0.07 sec, while that of C₁₀D₈ under identical conditions is 0.64 ± 0.07 sec. At this temperature 3-MP has the same viscosity (0.65 centipoise) as that of benzene at room temperature. It is believed that even these long lifetimes are dominated by impurity quenching mechanisms. Therefore it seems that the radiationless decay times of the lowest triplet states of simple aromatic hydrocarbons in liquid solutions are sensibly the same as those in the solid phase. A slight dependence of the phosphorescence lifetime on solvent viscosity was observed in the temperature region, -60° to -18°C. This has been attributed to the diffusion-controlled quenching of the triplet state by residual impurity, perhaps oxygen. Bimolecular depopulation of the triplet state was found to be of major importance over a large part of the triplet decay.

The lifetime of triplet C₁₀H₈ at room temperature was also measured in highly purified benzene by means of both phosphorescence and triplet-triplet absorption. The lifetime was estimated to be at least ten times shorter than that in 3-MP. This is believed to be due not only to residual impurities in the solvent but also to small amounts of impurities produced through unavoidable irradiation by the excitation source. In agreement with this idea, lifetime shortening caused by intense flashes of light is readily observed. This latter result suggests that experiments employing flash lamp techniques are not suitable for these kinds of studies.

The theory of radiationless transitions, based on Robinson's theory, is briefly outlined. A simple theoretical model which is derived from Fano's autoionization gives identical result.

Il. WHY IS CONDENSED OXYGEN BLUE?

The blue color of oxygen is mostly derived from double transitions. This paper presents a theoretical calculation of the intensity of the double transition (a ¹Δ_g) (a ¹Δ_g)←(X ³Σ_g^-) (X ³Σ_g^-), using a model based on a pair of oxygen molecules at a fixed separation of 3.81 Å. The intensity enhancement is assumed to be derived from the mixing (a ¹Δ_g) (a ¹Δ_g) _~~~ (X ³Σ_g^-) (X ³Σ_u^-) and (a ¹Δ_g) (¹Δ_u) _~~~ (X ³Σ_g^-) (X ³Σ_g^-). Matrix elements for these interactions are calculated using a π-electron approximation for the pair system. Good molecular wavefunctions are used for all but the perturbing (B ³Σ_u^-) state, which is approximated in terms of ground state orbitals. The largest contribution to the matrix elements arises from large intramolecular terms multiplied by intermolecular overlap integrals. The strength of interaction depends not only on the intermolecular separation of the two oxygen molecules, but also as expected on the relative orientation. Matrix elements are calculated for different orientations, and the angular dependence is fit to an analytical expression. The theory therefore not only predicts an intensity dependence on density but also one on phase at constant density. Agreement between theory and available experimental results is satisfactory considering the nature of the approximation, and indicates the essential validity of the overall approach to this interesting intensity enhancement problem.

Blue emission from Eu2+ -doped high silica glass by near-infrared femtosecond laser irradiation

Eu2+-doped high silica glass (HSG) is fabricated by sintering porous glass which is impregnated with europium ions. Eu2+-doped HSG is revealed to yield intense blue emission excited by ultraviolet (UV) light and near-infrared femtosecond laser. The emission profile obtained by UV excitation can be well traced by near-infrared femtosecond laser. The upconversion emission excited by 800 nm femtosecond laser is considered to be related to a two-photon absorption process from the relationship between the integrated intensity and the pump power. A tentative scheme of upconverted blue emission from Eu2+-doped HSG was also proposed. The HSG materials presented herein are expected to find applications in high density optical storage and three-dimensional color displays. (c) 2008 American Institute of Physics.

Blue green emission from a Cu+-Doped transparent material prepared by sintering porous glass

A colorless transparent, blue green emission material was fabricated by sintering porous glass impregnated with copper ions. The emission spectral profile obtained from Cu+ -doped high silica glass (HSG) by 267-mn monochromatic light excitation matches that obtained by pumping with an 800-nm femtosecond laser, indicating that the emissions in both cases come from an identical origin. The upconversion emission excited by 800-nm femtosecond laser is considered to be a three-photon excitation process. A tentative scheme of upconverted emission from Cu+ -doped HSG was also proposed. The glass materials presented herein are expected to find application in lamps, high density optical storage, and three-dimensional color displays.

The western blue groper (Achoerodus gouldii), a protogynous hermaphroditic labrid with exceptional longevity, late maturity, slow growth, and both late maturation and sex change

The western blue groper (Achoerodus gouldii) is shown to be a temperate protogynous hermaphrodite, which spawns between early winter and mid-spring. Because A. gouldii changes body color at about the time of sex change, its color can be used as a proxy for sex for estimating the size and age at sex change and for estimating growth when it is not possible to use gonads for determining the sex of this fish. The following characteristics make A. gouldii highly susceptible to overfishing: 1) exceptional longevity, with a maximum age (70 years) that is by far the greatest yet estimated for a labrid; 2) slow growth for the first 15 years and little subsequent growth by females; and 3) late maturation at a large total length (TL50 = 653 mm) and old age (~17 years) and 4) late sex change at an even greater total length (TL50 = 821 mm) and age (~35 years). The TL50 at maturity and particularly at sex change exceeded the minimum legal total length (500 mm) of A. gouldii and the lengths of many recreationally and commercially caught fish. Many of these characteristics are found in certain deep-water fishes that are likewise considered susceptible to overfishing. Indeed, although fishing effort for A. gouldii in Western Australia is not particularly high, per-recruit analyses indicate that this species is already close to or fully exploited.

Adjustment of ocean color sensor calibration through multi-band statistics

The band-by-band vicarious calibration of on-orbit satellite ocean color instruments, such as SeaWiFS and MODIS, using ground-based measurements has significant residual uncertainties. This paper applies spectral shape and population statistics to tune the calibration of the blue bands against each other to allow examination of the interband calibration and potentially provide an analysis of calibration trends. This adjustment does not require simultaneous matches of ground and satellite observations. The method demonstrates the spectral stability of the SeaWiFS calibration and identifies a drift in the MODIS instrument onboard Aqua that falls within its current calibration uncertainties.

Full-color emission from In2S3 and ln(2)S(3): Eu3+ nanoparticles

New observations on the luminescence Of In2S3 and europium-doped In2S3 nanoparticles show a green (5 10 nm) emission from In2S3 and In1.8Eu0.2S3 nanoparticles while a blue (425 nm) emission is observed from ln(1.6)Eu(0.4)S(3) nanoparticles. Both the blue and green emissions have large Stokes shifts of 62 and 110 nm, respectively. Excitation with longer-wavelength photons causes the blue emission to shift to a longer wavelength while the green emission wavelength remains unchanged. The lifetimes of both the green and blue emissions are similar to reported values for excitonic recombination. When doped with Eu3+, in addition to the broad blue and green emissions, a red emission near 615 nm attributed to Eu3+ is observed. Temperature dependences on nanoparticle thin films indicate that with increasing temperature, the green emission wavelength remains constant, however, the blue emission shifts toward longer wavelengths. Based on these observations, the blue emission is attributed to exciton recombination and the green emission to Indium interstitial defects. These nanoparticles show full-color emission with high efficiency, fast lifetime decays, and good stability; they are also relatively simple to prepare, thus making them a new type of phosphor with potential applications in lighting, flat-panel displays, and communications.

Color filter-less technology of LED back light for LCD-TV - art. no. 68410G

Back Light Unit (BLU) and Color Filter are the two key components for the perfect color display of Liquid Crystal Display (LCD) device. LCD can not light actively itself, so a form of illumination, Back Light Unit is needed for its display. The color filter which consists of RGB primary colors, is used to generate three basic colors for LCD display. Traditional CCFL back light source has several disadvantages, while LED back light technology makes LCD obtain quite higher display quality than the CCFL back light. LCD device based on LED back light owns promoted efficiency of display. Moreover it can generate color gamut above 100% of the NTSC specification. Especially, we put forward an idea of Color Filter-Less technology that we design a film which is patterned of red and green emitting phosphors, then make it be excited by a blue light LED panel we fabricate, for its special emitting mechanism, this film can emit RGB basic color, therefore replace the color filter of LCD device. This frame typically benefits for lighting uniformity and provide pretty high light utilization ratio. Also simplifies back light structure thus cut down the expenses.

Research on color matching of LED backlight for large-color-gamut LCD application - art. no. 68410Y

Comparing with the conventional CCFL (Cold Cathode Fluorescent Lamp) backlight, three-basic-color LEDs backlight has some advantages such as good color reproduction, long life and lead free etc. Theoretically, the color gamut is determined by x, y coordinates of the three basic colors in CIE chromaticity diagram, and the x, y coordinates of each basic color can derived from the relative spectrum distribution (RSD) of the LED. In this paper, the red, green and blue LEDs' RSD models are established to calculate and analyze the color gamut of a backlight. By simulating those models, the relationships that the color gamut of a LED backlight varies with each color are analyzed, and the optimum combination of three colors is obtained within the given wavelengths ranges. Moreover, the combinations of three colors for the gamut of 115% NTSC and 110% NTSC are plotted in pictures, respectively.

Manipulating charge-transfer character with electron-withdrawing main-group moieties for the color tuning of iridium electrophosphors

A new and synthetically versatile strategy has been developed for the phosphorescence color tuning of cyclometalated iridium phosphors by simple tailoring of the phenyl ring of ppy (Hppy=2-phenylpyridine) with various main-group moieties in [Ir(ppy-X)(2)(acac)] (X=B(Mes)(2), SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph). This can be achieved by shifting the charge-transfer character from the pyridyl groups in some traditional iridium ppy-type complexes to the electron-withdrawing main-group moieties and these assignments were supported by theoretical calculations.

Red-light-emitting iridium complexes with hole-transporting 9-arylcarbazole moieties for electrophosphorescence efficiency/color purity trade-off optimizationE

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations

Red-Light-Emitting Iridium Complexes with Hole-Transporting 9-Arylcarbazole Moieties for Electrophosphorescence Efficiency/ Color Purity Trade-off Optimization

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations. The highest occupied molecular orbital levels of these complexes are raised by the integration of a carbazole unit to the iridium isoquinoline core so that the hole-transporting ability is improved in the resulting complexes relative to those with I-phenylisoquinoline ligands. All of the complexes are highly thermally stable and emit an intense red light at room temperature with relatively short lifetimes that are beneficial for highly efficient organic light-emitting diodes (OLEDs).

Rapid synthesis of polyethylenimine-protected Prussian blue nanocubes through a thermal process

Polyethylenimine (PEI)-protected Prussian blue nanocubes have been simply synthesized by heating an acidic mixture of PEI, FeCl3, K3Fe(CN)(6), and KCI. The experiment results presented here demonstrate that the pH of the mixture plays an important role in controlling the shape and composition of the resultant product.