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Anthracene derivatives as broadband nonlinear optical materials: nonlinear absorption and excited-state dynamics analysis.

ABSTRACT: Two anthracene derivatives, AN-1 and AN-2, with different π-bridge lengths were designed and synthesized to investigate their optical nonlinearities. The nonlinear absorption (NLA) properties of both derivatives were measured via the femtosecond Z-scan technique with the wavelength range from 532 nm to 800 nm. The reverse saturable absorption (RSA) of both compounds results from two-photon absorption induced excited-state absorption (TPA-ESA). At all wavelengths, the reverse saturable absorption of AN-2 is superior to that of AN-1 due to a better molecular planarity for AN-2. Compared with the results of AN-1, the two-photon absorption coefficient of AN-2 can be increased by nearly 8 times (from 0.182 × 10^-2 cm GW^-1 for AN-1 to 1.42 × 10^-2 cm GW^-1 for AN-2) at 600 nm by extending the π-bridge. The evolution of femtosecond transient absorption (TA) spectra reveals the relaxation process from the singlet local excited-state (LES) to charge transfer state (CTS) for both compounds. The results imply that anthracene derivatives may be potential candidates for applications in future laser photonics.

SUBMITTER: Zhou W

PROVIDER: S-EPMC9054195 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Anthracene derivatives as broadband nonlinear optical materials: nonlinear absorption and excited-state dynamics analysis.

Zhou Wenfa W Fang Yu Y Wu Xingzhi X Han Yanbing Y Yang Junyi J Shen Lei L Song Yinglin Y

RSC advances 20200527 34

Two anthracene derivatives, AN-1 and AN-2, with different π-bridge lengths were designed and synthesized to investigate their optical nonlinearities. The nonlinear absorption (NLA) properties of both derivatives were measured <i>via</i> the femtosecond Z-scan technique with the wavelength range from 532 nm to 800 nm. The reverse saturable absorption (RSA) of both compounds results from two-photon absorption induced excited-state absorption (TPA-ESA). At all wavelengths, the reverse saturable abs ...[more]

PMID: 35520396

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Project description:A novel zinc phthalocyanine derivative [2(3), 9(10), 16(17), 23(24) tetrakis-4-((4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)ethynyl)phthalocyanine zinc(ii) (PBIPC)] was synthesized by incorporating a triphenyl imidazole moiety at its peripheral positions. The detailed mechanisms of absorption, emission, electrochemical, nonlinear optical (NLO) and photophysical (excited state dynamics) properties of PBIPC were explored. The absorption and emission properties of the compound were studied in different solvents. The incorporation of a triphenyl imidazole moiety at the peripheral position of the zinc phthalocyanine slightly broadened the Soret band. The emission studies revealed fluorescence quantum yields to be in the range of 0.11-0.22. The time-resolved fluorescence data established the radiative lifetimes to be in the nanosecond range. The oxidation and reduction processes were found to be ring centered, which were studied using the cyclic voltammetry (CV) technique. The energy optimized structures and HOMO-LUMO levels were calculated using DFT, TD-DFT analysis and were employed by means of hybrid functional theory (B3LYP) at 6-31G (d,p) basis set in the Gaussian 09 package. Two-photon absorption was observed in the NLO studies performed in the visible wavelength range of 600-800 nm while the nonlinear absorption was dominated by three- and four-photon absorption processes in the NIR wavelength range (1.0-1.5 μm). The molecule exhibited self-focusing behavior for all the wavelengths. Finally, the excited state dynamics of the title molecule PBIPC were investigated using femtosecond transient absorption spectroscopy and the results obtained were understood on the basis of a simple three kinetic model, for excitation wavelengths of 400 nm (Soret band) and 650 nm (Q-band). Both the spectra demonstrated a broad positive transient absorption (TA) data which overlapped with the ground state bleach (GSB), which in turn displayed a red shift over a delay of ∼2 ns. The lifetimes revealed a possibility of intersystem crossing (τ > 1 ns) owing to the triplet state transition.

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Anthracene derivatives as broadband nonlinear optical materials: nonlinear absorption and excited-state dynamics analysis.

Publications

Anthracene derivatives as broadband nonlinear optical materials: nonlinear absorption and excited-state dynamics analysis.

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