Metalated porphyrin-napthalimide based donor-acceptor systems with long-lived triplet states and effective three-photon absorption

Ahmed, Md Soif and Biswas, Chinmoy and Raavi, Sai Santosh Kumar and et al, . (2023) Metalated porphyrin-napthalimide based donor-acceptor systems with long-lived triplet states and effective three-photon absorption. Journal of Photochemistry and Photobiology A: Chemistry, 435. ISSN 1010-6030

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Abstract

Porphyrin applications are primarily related to electronic transitions across a broad spectrum. In this context, understanding the excited state electron dynamics is necessary in such chromophores. Herein, we report the ultrafast photophysical characterization of one free base and three transition metallated porphyrin - napthalimide based donor - acceptor systems (PN-Fb, PN-Ni, PN-Cu, and PN-Zn) in dichloromethane (DCM) solution using transient absorption spectroscopy (TAS) in the spectral range of 430–780 nm by the Soret band excitation at 400 nm. The different rate constants were extracted using a target model analysis of the collected transient absorption spectra and established a consistent photophysical model of molecular excited state population relaxations. The photophysical model consisted of the following various processes: (a) internal conversion in the range of 215–400 fs, (b) vibrational relaxation in the range of 1.35–62 ps, and (c) singlet state relaxation times in the range of 0.17–2.06 ns, and finally (d) 0.03–10 μs was attributed to the triplet state lifetimes. We have also measured the nonlinear optical properties of these molecules by the open and closed aperture Z-scan studies, which was carried out by 800 nm, 70 fs photoexcitation. The theoretical fittings to the experimental data resulted in an effective three-photon absorption coefficient and positive nonlinear refractive index. Further, from the Z-scan data, the second hyperpolarizability of the molecules was calculated, and the values were 10-31 esu. Additionally, complete optimization of individual structures and construction of these PN systems was achieved using density functional theory (DFT) calculations and the obtained results were found to be consistent with the experimental observations. © 2022

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IITH Creators:

IITH Creators	ORCiD
Raavi, Sai Santosh Kumar	http://orcid.org/0000-0002-2496-9233

Item Type:

Article

Additional Information:

MSA and RSSK acknowledge the financial support of BRICS/PilotCall2/IEEE-OSC/2018 (G), and CRG/2019/003197, respectively. D.B. acknowledge the funding support from PMRF. B. B. acknowledge DST-Inspire for fellowship. S. P. thanks the Department of Science and Technology and Inspire program (DST/INSPIRE/04/2015/001457) for funding support. Venugopal Rao Soma thanks DRDO, India for financial support through ACRHEM.

Uncontrolled Keywords:

DFT; Excited-state dynamics; Femtosecond Z-scan; Optical limiting; Porphyrin – napthalimide; Transient absorption

Subjects:

Physics

Divisions:

Department of Physics

Depositing User:

. LibTrainee 2021

Date Deposited:

04 Nov 2022 10:18

Last Modified:

04 Nov 2022 10:18