Excited State Dynamics and Nonlinear Absorption of a Pyrazinoporphyrazine Macrocycle Carrying Externally Appended Pyridine Rings

• Published in: The journal of physical chemistry. B 2006-12, Vol.110 (48), p.24354-24360
• Main Authors: Villano, Massimo, Amendola, Vincenzo, Sandonà, Giancarlo, Donzello, Maria Pia, Ercolani, Claudio, Meneghetti, Moreno
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp0647683

The multiphoton absorption properties of the tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato(monoacquo)-Mg(II) complex [Py8TPyzPzMg(H2O)] (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, [Py8TPyzPzMg(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.