[60]Fullerene-porphyrin [n]pseudorotaxanes: self-assembly, photophysics and third-order NLO response.

By means of different spectroscopic techniques, we investigate a novel series of porphyrin derivatives (H2TPP), connected to dibenzo-24-crown-8 (DB24C8) moieties, which undergo self-assembly with different methano[60]fullerene units bearing dibenzylammonium (DBA) cations. The formation of both [2] and [3]pseudorotaxanes was proved by means of NMR, UV-Vis-NIR absorption and emission spectroscopies. With the support of molecular modelling studies, spectroscopic investigations showed the presence of a secondary interaction between the porphyrin and the C60 chromophores leading to the formation of different types of "face-to-face" assemblies. Remarkably, investigations of the non-linear optical response of these supramolecular systems showed that individual porphyrin and fullerene derivatives exhibit significantly lower second hyperpolarizability values when compared to their pseudorotaxanes functionalised counterparts. This proves that this class of supramolecular materials possesses relevant NLO response, which strongly depends on the structural arrangement of the chromophores in solution.

Ultrafast third order nonlinearities of organic solvents.

The third order nonlinear optical parameters of a variety of organic solvents are determined under picosecond and femtosecond laser irradiation. Z-scan measurements have been carried out at 35 ps, 532 nm and at 40 fs, 800 nm, while Optical Kerr Effect studies were performed at 35 ps, 532 nm. The target of the present work is to provide a reference of the nonlinear optical response of various widely used organic solvents under the same experimental conditions and render feasible the direct comparison between their nonlinearities.

Fluoro-graphene: nonlinear optical properties.

In the present work, we report on the investigation of the third-order nonlinear optical response of graphene fluoride dispersed in DMF and also of fluorosurfactant-stabilized graphene fluoride dispersed in water under visible (532 nm) and infrared (1064 nm), picosecond and nanosecond laser excitation. Both graphene derivatives were found to exhibit large nonlinear optical response, while significant differences on their nonlinear optical response have been observed (e.g. different sign of nonlinear refraction and absorption). These findings highlight the important role of the degree of fluorination of the graphene sheets on their optical and electronic properties. Furthermore, DMF dispersed graphene fluoride was found to exhibit important broadband optical limiting action under nanosecond laser excitation, making it promising candidate for optical limiting applications.

Aqueous dispersions of C60 fullerene by use of amphiphilic block copolymers: preparation and nonlinear optical properties.

The dispersion of the otherwise insoluble C60 fullerene in water is discussed. Amphiphilic block copolymers, namely, polystyrene-b-polyethylene oxide (PS-PEO), were found to be able to disperse C60 in aqueous solutions, where the polymer forms micelles with a hydrophobic PS core. The preparation protocol of the final solutions was found to play a crucial role in the ability of the block copolymer to disperse the C60 molecules. The C60 containing aggregates were studied using optical spectroscopy, light scattering, and scanning electron microscopy. In addition, their optical limiting action and nonlinear optical properties under visible nanosecond laser excitation were studied and compared with that of C60-toluene solutions.