RESUMEN
Functionalized distyrylbenzene analogs and , bearing a tris-(2-pyridylmethyl)amine-based receptor for Zn(2+), were synthesized by a Horner-Emmons-Wittig coupling reaction. It has been found that Zn(2+) complexation induces changes in the linear absorption spectrum that enhance a nonlinear sequential two-photon absorption of nanosecond pulses at 532 nm. This absorption was also found to depend on the nature of the substituent at the side benzene ring of the styrylbenzene structure.
Asunto(s)
Derivados del Benceno/síntesis química , Compuestos Organometálicos/química , Estirenos/química , Zinc/química , Derivados del Benceno/química , Estructura Molecular , FotonesRESUMEN
The multiphoton absorption properties of the tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato(monoacquo)-Mg(II) complex [Py(8)TPyzPzMg(H(2)O)] (1) are reported and interpreted. The nonlinear optical behavior of 1 and the characterization of the excited states important for the nonlinear absorption process were studied at the pump frequency of the second harmonic generation of a Nd:YAG laser in the nanosecond time regime. It was found that complex 1 shows a very good optical limiting performance at 532 nm, which derives from two processes: (a) a reverse-saturable absorption process, which involves a triplet excited state at low intensities, and (b) a two-photon absorption process at higher intensities, which is due to the formation of the radical monoanion of 1, [Py(8)TPyzPzMg(H2O)](.-), during the photoreduction of the triplet state. The participation of a monoanion in determining the overall nonlinear absorption behavior of 1 is found, for the first time, for a tetrapyrrolic system. One can deduce that the involvement of the monoanion derives from the electron-withdrawing effect of the dipyridinopyrazino fragments externally attached to the porphyrazine core which make the reduced form of 1 easily accessible. These results suggest a modification of tetrapyrrolic systems with new nonlinear absorption properties.
