Ultrafast photophysical and nonlinear optical properties of novel free base and axially substituted phosphorus (V) corroles

The progression in synthetic procedures over the last two decades gave admittance to a wide variety of corroles for suitable potential applications such as photovoltaics, photonics, and bio-imaging. In this communication, we present results from our investigations of ultrafast photophysical processes and third-order nonlinear optical properties of newly synthesized donor-acceptor based free-base [(C6F5)(3)] and phosphorus [P-(OH)(2)(C6F5)(3)] corroles. The global analysis of the femtosecond transient absorption data based on the compartmental model revealed the corresponding time constants of several photophysical processes such as (a) internal conversion (tau(IC)) in the 260-280 fs range (b) vibrational relaxation (tau(VR)) in the 2.5-5 ps range and (c) nonradiative relaxation times (tau(nr)) in the 4.15-7.6 ns range and finally (d) triplet lifetimes in the range of 25-50 mu s. The two-photon absorption (TPA) cross-section measurements were performed using the femtosecond, kHz pulse Z-Scan technique at 600 nm and 800 nmand the retrieved TPA cross-section values were in the range of similar to 10(2) GM. Degenerate four-wave mixing measurements illustrated a large third-order nonlinear optical susceptibility chi((3)) with a magnitude of 6.9 x 10(-14) esu and instantaneous (sub-picosecond) response, suggesting a pure electronic contribution to the nonlinearity of these corroles. The discoveries from this study may help further to extend the capability of corroles as NLO materials for photonic applications. (C) 2020 Elsevier B.V. All rights reserved.