RESUMO
The dynamics of excited states in α,ω-dinaphthylpolyyne, a class of linear sp-carbon chains, has been investigated by ultrafast transient absorption spectroscopy and DFT//TDDFT calculations. We show that the role of molecular conformers, in which end-capped naphthalene rings are planar or perpendicular to the polyyne plane, is fundamental for understanding both the steady state properties, such as UV-Vis absorption spectra and vibronic transitions, and the ultrafast transient absorption features. In particular, we observed in one of the conformers the ultrafast formation of a narrow photo-induced absorption band rising within 30 ps. This band can be assigned to an inter-system crossing event leading to the formation of triplet excited states.
RESUMO
Conjugated organic materials in the solid state are generally amorphous or polycrystalline, with local order only achieved in mesoscopic domains with size ranging from a few tens to a few hundreds of nanometres. Understanding the interplay between mesoscopic order and macroscopic behaviour of these materials calls for a spatially resolved study of their optical properties. Near-field scanning optical microscopy allows one in principle to beat the diffraction limit in optical imaging. A quantitative measurement of nanoscale absorption spectra is, however, complicated by the difficulty of obtaining broadband near-field illumination with sufficiently high intensity. Here we demonstrate a near-field spectrometer with 100-nm spatial resolution based on an ultrabroadband Ti : sapphire oscillator coupled to an aperture-based near-field scanning optical microscopy, enabling structural phase-selective imaging of organic materials at the nanoscale. In polycrystalline phtalocyanine films we can distinguish between the crystalline and the amorphous phase, thus providing previously unavailable information on their mesoscopic texture.
RESUMO
Femtosecond electric-field-assisted pump-probe measurements are a new approach to the study of fundamental processes within organic optoelectronic devices. Here we report a detailed study of organic light-emitting diodes based on poly(9,9-dioctylfluorene), using both temporal and spectral information to investigate polaron generation, due to field-induced singlet dissociation, and their subsequent recombination. The fundamental event in electroluminescence is time resolved: we find that initially free polarons coalesce into intermediate pairs of both singlets and triplets multiplicity which subsequently decay into the neutral state. Our results indicate that the efficiency of singlet formation, beta approximately 0.7, is much higher than expected from simple state degeneracy arguments (beta approximately 0.25).
RESUMO
A series of oligomers analogous to poly(p-phenylenevinylene) (PPV), combining naphthalene and benzene as aromatic units, have been synthesized by a Knoevenagel reaction. By measuring UV/Vis spectra, photoluminescence (PL) and electroluminescence (EL), we studied the influence of the position of the naphthalene unit as well as the steric and electronic influences of cyano and alkyloxy substituents on the luminescent properties of these compounds.
