RESUMO
This study of the optoelectronic properties of blue light-emitting diodes under direct current stress. It is found that the electroluminescence intensity increases with duration of stress, and the efficiency droop curves illustrated that the peak-efficiency and the peak-efficiency-current increases and decreases, respectively. We hypothesize that these behaviors mainly result from the increased internal quantum efficiency.
RESUMO
Oligothiophenes incorporating MM quadruple bonds have been prepared from the reactions between Mo(2)(TiPB)(4) (TiPB = 2,4,6-triisopropyl benzoate) and 3',4'-dihexyl-2,2'-:5',2''-terthiophene-5,5''-dicarboxylic acid. The oligomers of empirical formula Mo(2)(TiPB)(2)(O(2)C(Th)-C(4)(n-hexyl)(2)S-(Th)CO(2)) are soluble in THF and form thin films with spin-coating (Th = thiophene). The reactions between Mo(2)(TiPB)(4) and 2-thienylcarboxylic acid (Th-H), 2,2'-bithiophene-5-carboxylic acid (BTh-H), and (2,2':5',2''-terthiophene)-5-carboxylic acid (TTh-H) yield compounds of formula trans-Mo(2)(TiPB)(2)L(2), where L = Th, BTh, and TTh (the corresponding thienylcarboxylate), and these compounds are considered as models for the aforementioned oligomers. In all cases, the thienyl groups are substituted or coupled at the 2,5 positions. Based on the x-ray analysis, the molecular structure of trans-Mo(2)(TiPB)(2)(BTh)(2) reveals an extended Lpi-M(2)delta-Lpi conjugation. Calculations of the electronic structures on model compounds, in which the TiPB are substituted by formate ligands, reveal that the HOMO is mainly attributed to the M(2)delta orbital, which is stabilized by back-bonding to one of the thienylcarboxylate pi* combinations, and the LUMO is an in-phase combination of the thienylcarboxylate pi* orbitals. The compounds and the oligomers are intensely colored due to M(2)delta-thienyl carboxylate pi* charge transfer transitions that fall in the visible region of the spectrum. For the molybdenum complexes and their oligomers, the photophysical properties have been studied by steady-state absorption spectroscopy and emission spectroscopy, together with time-resolved emission and transient absorption for the determination of relaxation dynamics. Remarkably, THF solutions the molybdenum complexes show room-temperature dual emission, fluorescence and phosphorescence, originating mainly from (1)MLCT and (3)MM(deltadelta*) states, respectively. With increasing number of thienyl rings from 1 to 3, the observed lifetimes of the (1)MLCT state increase from 4 to 12 ps, while the phosphorescence lifetimes are approximately 80 micros. The oligomers show similar photophysical properties as the corresponding monomers in THF but have notably longer-lived triplet states, approximately 200 micros in thin films. These results, when compared with metallated oligothiophenes of the later transition elements, reveal that M(2)delta-thienyl pi conjugation leads to a very small energy gap between the (1)MLCT and (3)MLCT states of <0.6 eV.
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L-ascorbic acid quenches singlet (1 delta g) molecular oxygen in aqueous media (pH 6.8 for [1H]H2O and pD 7.2 for [2H]D2O) as measured directly by monitoring (0,0) 1 delta g leads to 3 sigma-g emission at 1.28 micron. Singlet oxygen was generated at room temperature in the solutions via photosensitization of sodium chrysene sulfonate; this sulfonated polycyclic hydrocarbon was synthesized to provide a water soluble chromophore inert to usual dye-ascorbate photobleaching. A marked isotope effect is found; kHQ2O is 3.3 times faster than kDQ2O, suggesting ascorbic acid is chemically quenching singlet oxygen.
Assuntos
Ácido Ascórbico , Oxigênio , Deutério , Óxido de Deutério , Cinética , Oxirredução , Fotoquímica , Oxigênio Singlete , ÁguaRESUMO
The synthesis and photophysics of 4-formyl-4'-N,N-dimethylamino-1,1'-biphenyl are reported. The emission spectrum in various solvent polarities demonstrates solvatochromism, indicating that the fluorescence originates from an electronically excited species with a strong charge transfer character. The change in Δ[Formula: see text] [[Formula: see text] max(absorption) -[Formula: see text] max(emission)] varies from â¼1500 cm(-1) inn-heptane to as much as â¼7500 cm(-1) in acetonitrile. In protic solvents, the unusual excitation energy-dependent steady-state emission (red edge effect), resulting from solvent dielectric relaxation, was observed in media with a low viscosity. The large Stokes-shifted and high-yield fluorescence led to the observation of the efficient lasing action. The frequency tunability of the laser output is strongly solvent dependent, generating a new charge transfer laser dye in the blue-green region.