Observation of the two-photon transition enhanced first hyperpolarizability spectra in cinnamaldehyde derivatives: A femtosecond regime study.

The application of nonlinear optical effects in optoelectronic devices is still scarce because the irradiance threshold necessary to induce a specific effect is very high. In this context, knowing the frequency-resolved first order molecular hyperpolarizability (ß) is essential to identifying regions where this response is intense enough to allow for applications in commercial devices. Thus, herein, we have determined the ß spectral dependence of five new push-pull cinnamylidene acetophenone derivatives using femtosecond laser-induced Hyper-Rayleigh Scattering (HRS). A considerable increase in ß values was observed in molecules. We found remarkable ß values in regions near the two-photon resonance, which are mediated by electron withdrawing and donating groups. This effect was mapped using wavelength-tunable femtosecond Z-scan technique. Furthermore, it was modeled in light of the sum-over-states approach for the second- and third-order nonlinearities. Finally, our outcomes suggest a strategy to obtain large ß values mediated by the 2PA transition.

Mechanism of the Zn(II)Phthalocyanines' Photochemical Reactions Depending on the Number of Substituents and Geometry.

In this work, the synthesis and the nonlinear absorption and population dynamics investigation of a series of zinc phthalocyanines (ZnPcs) dissolved in chloroform are reported. In order to determine the relevant spectroscopic parameters, such as absorption cross-sections of singlet and triplet excited states, fluorescence relaxation times, intersystem crossing, radiative decay and internal conversion, different optical and spectroscopic techniques were used. By single pulse and pulse train Z-scan techniques, respectively, singlet and triplet excited states' absorption cross-section were determined at 532 nm. Furthermore, the intersystem crossing time was obtained by using both techniques combined with the fluorescence lifetime determined by time-resolved fluorescence. The radiative and internal conversion rates were determined from the fluorescence quantum yield of the samples. Such spectroscopy parameters are fundamental for selecting photosensitizers used in photodynamic therapy, as well as for many other applications.

Femtosecond Two-Photon Absorption Spectroscopy of Poly(fluorene) Derivatives Containing Benzoselenadiazole and Benzothiadiazole.

We have investigated the molecular structure and two-photon absorption (2PA) properties relationship of two push-pull poly(fluorene) derivatives containing benzoselenadiazole and benzothiadiazole units. For that, we have used the femtosecond wavelength-tunable Z-scan technique with a low repetition rate (1 kHz) and an energy per pulse on the order of nJ. Our results show that both 2PA spectra present a strong 2PA (around 600 GM (1 GM = 1 × 10-50 cm4·s·photon-1)) band at around 720 nm (transition energy 3.45 eV) ascribed to the strongly 2PA-allowed 1Ag-like → mAg-like transition, characteristic of poly(fluorene) derivatives. Another 2PA band related to the intramolecular charge transfer was also observed at around 900 nm (transition energy 2.75 eV). In both 2PA bands, we found higher 2PA cross-section values for the poly(fluorene) containing benzothiadiazole unit. This outcome was explained through the higher charge redistribution at the excited state caused by the benzothiadiazole group as compared to the benzoselenadiazole and confirmed by means of solvatochromic Stokes shift measurements. To shed more light on these results, we employed the sum-over-states approach within the two-energy level model to estimate the maximum permanent dipole moment change related to the intramolecular charge transfer transition.