RESUMEN
This study describes the synthesis of new pyromellitic diimide (PMDI) derivatives obtained in good yields from the reaction between pyromellitic dianhydride and aminobenzazoles reactive to proton-transfer in the excited state (ESIPT). In this investigation, a non-ESIPT PMDI was also prepared for comparison. These compounds presented absorption maxima in the ultraviolet region attributed to the allowed 1π-π* electronic transitions. Redshifted absorptions were observed for the ESIPT compounds (3b-3c) due to their π-extended conjugation if compared to the non-ESIPT dye (3a). The compounds presented fluorescence emissions between 300 and 600 nm, dependent on the solvent polarity and their chemical structures. While compound 3a presents a single emission, a dual fluorescence could be observed for compounds 3b-3c. As expected for ESIPT compounds, the emission at higher energies could be related to the excited enol conformer (E*), and the emission with a large Stokes shift was attributed to the keto tautomer (K*). All compounds presented fluorescence emission in the solid state, whereas the ESIPT derivatives presented redshifted emissions with a large Stokes shift, as expected. Cyclic voltammetry was employed to investigate the electrochemical properties of these compounds. The HOMO and LUMO energy levels were estimated at -5.40 to -5.00 eV and -2.84 to -2.62 eV, and good thermal stability (Td > 150 °C) was observed. Quantum chemical calculationsusingTD-DFT and DFT were performed to investigate the electronic and photophysical features of the molecules.
RESUMEN
Considering the relevance of room temperature phosphorescent (RTP) materials, we discuss the influence of donor and acceptor groups substituted on to a twisted three-fold symmetric hydrocarbon homotruxene, which presents a persistent RTP, even in the absence of donor or acceptor moieties, under ambient conditions as a result of the twisted π-system. Compared to a fluorine acceptor, a donor methoxy group increases the phosphorescence decay rate in solution, while in the solid-state, molecular aggregation and packing yield a very persistent phosphorescence visible by the eye. The RTP of the intrinsically apolar homotruxene is found to be modulated by polar substituents, whose main impact on the solid-state emission is due to altered packing in the crystal.
RESUMEN
Speeding up the phosphorescence channel in luminescent copper(I) complexes has been extremely challenging due to the copper atoms relatively low spin-orbit coupling constant compared to heavier metals such as iridium. Here, we report the synthesis and characterization of three mononuclear copper(I) complexes with diimines, triphenylphosphine, and iodide ligands to evaluate the effect of the copper-iodide (Cu-I) moiety into the phosphorescence decay pathway. Temperature-dependent photophysical studies revealed combined thermally activated delayed fluorescence and phosphorescence emission, with a phosphorescence decay rate of the order of 104 s-1. Density functional theory calculations indicate very high spin-orbit coupling matrix elements between the low-lying states of these complexes. Compared to the classical [Cu(phen)(POP)]+, our results demonstrate that Cu-I is a versatile moiety to speed up the phosphorescence decay pathway in about one order of magnitude, and it can be prepared by a simplified synthetic route with few synthetic steps. Furthermore, the SOC matrix elements and the phosphorescence decay rates of these complexes are comparable to those of extensively applied coordination complexes based on heavier metals, making them a promising alternative as active layers of organic light-emitting diodes.
RESUMEN
Halogenation of a twisted three-fold symmetric hydrocarbon with F, Cl or Br leads to strong modulation of triplet-triplet annihilation and dual phosphorescence, one thermally activated and the other very persistent and visible by eye, with different relative contributions depending on the halide. The room temperature phosphorescence is highly unusual given the absence of lone-pair-contributing heteroatoms. The interplay between the spin-orbit coupling matrix elements and the spatial configuration of the triplet state induces efficient intersystem crossing and thus room temperature phosphorescence even without relying on heteroatomic electron lone pairs. A ninefold increase of the ISC rate after introduction of three bromine atoms is accompanied by a much higher 34-fold increase of phosphorescence rate.
RESUMEN
A systematic study of the synthetic procedure to improve quantum efficiency of luminescent hybrid perovskite QDs through ligand-assisted precipitation method is presented. Particularly, the influence of the dielectric constant and dipole moment of the antisolvent on the reaction time and the photophysical properties of the QDs is highlighted. After evaluating the influence of antisolvents and optimizing experimental parameters such as reaction time and Pb excess of the precursor, colloidal crystalline MAPbBr3QDs with exceptionally high absolute quantum yield up to 97.7% in solution and 69.1% in solid film were obtained. Finally, MAPbBr3QDs precipitated from anisole were processed like UV-curable nanocomposite as efficient down conversion layer resulting in very narrow green emission light-emitting diode.
RESUMEN
The dehydrating cyclotrimerization of 1-tetralone in the presence of titanium tetrachloride at high temperatures leads to homotruxene, a nonplanar arene in which the twist angles between its three outer benzene rings and the central benzene are stabilized by ethylene bridges. This non-planar configuration allows for pronounced spin-orbit coupling and a high triplet energy, leading to room-temperature phosphorescence in air with a lifetime of 0.38â s and a quantum yield of 5.6 %, clearly visible to the human eye after switching off the excitation. Triplet-triplet annihilation is found to simultaneously lead to a substantial delayed fluorescence, unprecedented from a pure hydrocarbon at ambient conditions, with a lifetime of 0.11â s.
