We report a strongly interacting new dendrimer system with an extended spectroscopic unit (coherent domain) beyond the trimer configuration. This report focuses on the mechanism of enhancement of the two-photon absorption (TPA) response of this material as a function of the dendrimer generation number. This enhancement is strongly correlated to the size and geometry of the spectroscopic unit in a strongly interacting macromolecular system. These systems are investigated by a wide variety of time-resolved spectroscopy methods including time-resolved fluorescence, transient absorption, three-pulse photon echo peak shift measurements as well as TPA cross section measurements. The extensive combination of modern spectroscopic methods strongly indicates that the spectroscopic unit (domain) in high generations covers the G1 (nine linear building blocks) and exceeds the trimer size.

In order to understand the dependence of photoinduced initial processes on thermal annealing, the femtosecond time-resolved fluorescence dynamics of regioregular poly(3-hexylthiophene) (P3HT) in (thermally) annealed P3HT/[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) blend films has been studied by using the fluorescence up-conversion technique. For comparison, a P3HT solution, pristine P3HT, and unannealed P3HT/PCBM blend films have been investigated as well. The fluorescence dynamics of the P3HT solution showed wavelength dependence. Excitation energy transfer between the segments and torsional relaxation possibly occurred in a time scale of several ps in the solution. Observed rise times at longer wavelength emission suggested the formation of these relatively lower emission states (at 650 and 700 nm). Charge transfer (or excitonic quenching) was the dominant process in the fs time scale with emission at 650 nm in the unannealed blend film. In the annealed blend film, the charge transfer (334 fs) and downhill relaxation (942 fs) of self-trapped (dynamic localized) excitons were competitive processes due to the well aligned nanodomains in the P3HT/PCBM blend films. There were different charge transfer rates at different excited states (650 and 700 nm) in the annealed film. The charge transfer process occurred faster at a lower excited state, and a stronger electronic and vibrational coupling in the annealed P3HT/PCBM films was revealed within these measurements as well. The ultrafast anisotropy decays suggested that a strong and ultrafast reorientation of the molecular dipole moments occurred at excited states. The anisotropy decay was mainly determined by the ultrafast process, whereas the energy could continuously migrate along or between P3HT chains in a time scale of ∼100 ps. The ultrafast process suggested that there was an excitation delocalization associated with vibrational modes, as was consistent with the observation from steady-state measurements. On the basis of the understanding of the mechanisms above, the optimized cell performance has been established.

Sonochemical decomposition of Fe(CO)5 was carried out in the presence of different surfactants. The reactions give stable colloids of undecenoate, dodecyl sulfonate, and octyl phosphonate coated Fe2O3 nanoparticles of 5-16 nm in diameter. The ionic binding of the surfactants to the nanoparticle surfaces was confirmed by FTIR spectroscopy. Electron paramagnetic resonance measurements, magnetization curves, and zero-field cooled and field cooled studies indicate that the as-prepared amorphous nanoparticles are superparamagnetic. These studies show that the phosphonate-coated nanoparticles behave in a strikingly different manner from the other particles. It is proposed that the extra negative charge on the phosphonate, as compared to the carboxylate and sulfonate groups, makes it a strong bridging bidentate ligand, resulting in the formation of strong ionic bonds to the surface Fe 3+ ions, which decreases the number of unpaired spins, possibly through a double superexchange mechanism through a Fe 3+ -O-P-O-Fe 3+ pathway.