Nonlinear absorption dynamics of Zn(2+), Cu(2+), and Ni(2+) tetrapyridyl porphyrins in chloroform/methanol solutions were investigated at 532 nm with the Z-scan technique. Additional techniques such as UV-vis absorption spectroscopy and time-resolved fluorescence were used to obtain parameters that are important for the analysis of the population dynamics. A marked difference was observed in the nonlinear absorption and excited-state dynamics of closed (ZnTPyP)- and open-shell metalloporphyrins (CuTPyP and NiTPyP). ZnTPyP presents a reverse saturable absorption whose dynamics can be completely described by means of a simple five-energy-level diagram. On the other hand, CuTPyP and NiTPyP have a different excited-state dynamics, presenting a saturable absorption behavior and faster relaxation rates that were attributed to the presence of unfilled d shells of the central ion.
Two-photon induced excited-state absorption and optical limiting properties in a chiral polymer Appl. Phys. Lett. 102, 043308 (2013); 10.1063/1.4790391Spectral dependence of third order nonlinear optical susceptibility of zinc phthalocyanine This work employs the Z-scan technique with 120 fs pulses to investigate the singlet excited state absorption spectra of tetrapyridyl and tetrasulfonatophenyl porphyrins. We have used a three-energy-level model to adjust Z-scan curves in order to obtain the singlet excited absorption cross section from 460 to 800 nm. Starting from these values, we determine the spectra of the ratio between excited and ground singlet state absorption cross sections, whose values are as good as the best found in the literature for reverse saturable absorbers. The results obtained point these porphyrins as good candidates for applications in optical limiting of ultrashort pulses.
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