Nonlinear optical absorption and refraction properties of fluorinated trans-dicationic pyridinium porphyrin and its metal complexes

Vijisha, M.V.; Ramesh, Jagadeesan; Arunkumar, Chellaiah; Chandrasekharan, K.

doi:10.1016/j.optmat.2019.109474

Cited by 17 publications

(12 citation statements)

References 46 publications

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“…Kiran et al reported third-order optical nonlinearities with enhanced features of optical limiting behavior in 5,10,15,20-(tetratolyl)porphyrinatophosphorus(V) dichloride, which has large ESA . Similarly, Vijisha et al reported the ESA-assisted enhanced nonlinear absorption in metalloporphyrins, which stems from the extended delocalization due to heavy atom effects . In general, β-TCBD-appended porphyrins ( 2 – 6 ) exhibited higher two-photon absorption cross-section values as compared to H 2 PE 2 ( 1 ) due to the strong electron-withdrawing nature of the TCBD unit and extended π-conjugation.…”

Section: Resultsmentioning

confidence: 93%

“…47 Similarly, Vijisha et al reported the ESA-assisted enhanced nonlinear absorption in metalloporphyrins, which stems from the extended delocalization due to heavy atom effects. 48 In general, β-TCBDappended porphyrins (2−6) exhibited higher two-photon absorption cross-section values as compared to H 2 PE 2 (1) due to the strong electron-withdrawing nature of the TCBD unit and extended π-conjugation.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

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β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

et al. 2021

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A series of β-TCBD (1,1,4,4-tetracyano-buta-1,3diene)-appended porphyrins, M-TCBD (M = 2H, Co(II), Ni(II), Cu(II), and Zn(II)), was synthesized from 2,3-diphenylethynyl-12nitro-meso-tetraphenylporphyrin, H 2 -PE 2 , and characterized by various spectroscopic techniques and electrochemical studies. The reaction proceeds via [2 + 2] cycloaddition and retroelectrocyclization reactions of tetracyanoethylene (TCNE) with H 2 -PE 2 . The observed unusual reduction potentials in the cyclic voltammograms of the synthesized porphyrins in the range of −0.06 to −0.10 V are the consequence of the TCBD moiety present at the β-position of the porphyrin macrocycle. Notably, these porphyrins exhibited three porphyrin ring-centered reductions due to extended π-conjugation. The higher nonlinear optical response exhibited by the M-TCBD series as compared to the precursor (H 2 -PE 2 ) was attributed to the existence of intramolecular charge transfer and enhanced polarization in the M-TCBD series. The single-beam femtosecond Z-scan measurements were performed to elucidate the third-order nonlinear optical properties, and the temporal response of these porphyrin molecules was investigated using optical pump−probe spectroscopy to study the excited state absorption dynamics. Zscan measurements revealed that Co-TCBD exhibited a higher nonlinear optical response as compared to free base porphyrins. The two-photon absorption coefficient (β) and the imaginary part of third-order nonlinear optical susceptibility (χ (3) ) were obtained from the open aperture experiment, whereas the close aperture experiment delivered the magnitude and the sign of the nonlinear refractive index (n 2 ) and the real part of χ (3) . Furthermore, the femtosecond transient absorption spectroscopy revealed a faster relaxation dynamics of various absorption processes in a picosecond timescale. The excellent optical limiting threshold (1.90−2.33 × 10 15 W/m 2 ) of the synthesized porphyrins makes them good materials for laser protection and high-power laser operation.

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Section: Resultsmentioning

confidence: 93%

Section: ■ Results and Discussionmentioning

confidence: 98%

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

et al. 2021

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“…All CA scans exhibit a valley-peak configuration curve suggesting a positive nonlinear refractive index of pure Kerr-type electronic origin. 94,101 The Kerr nonlinearity is responsible for the self-focusing effect that arises from the high intensity of femtosecond laser pulse propagation. 94,102,103 The nonlinear refractive index (n 2 ) and Re.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Unsymmetrically β-Functionalized π-Extended Porphyrins: Synthesis, Spectral, Electrochemical Redox Properties, and Their Utilization as Efficient Two-Photon Absorbers

et al. 2022

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Two new series of unsymmetrically β-functionalized porphyrins, MTPP(NO 2 )MA (1M), (MA = methyl acrylate) and MTPP(NO 2 )MB (2M) (MB = mono-benzo) (where M = 2H, Co(II), Ni(II), Cu(II) and Zn(II)), were synthesized and characterized by various spectroscopic techniques. The saddle shape conformation of ZnTPP(NO 2 )MAPy and ZnTPP(NO 2 )MB was confirmed by single-crystal X-ray analysis. Density functional theory (DFT) calculation revealed that NiTPP(NO 2 )MB has a severe nonplanar geometry possessing a high magnitude of ΔC β = ±0.727 Å and Δ24 = ±0.422 Å values among all other porphyrins. Synthesized β-substituted porphyrins exhibited red-shifted B-and Q-bands corresponding to their parent molecule due to the electron-withdrawing peripheral substituents. Notable redshift (Δλ max = 50−60 nm) in electronic spectral features and with weakintensity emission spectral features were observed for the free-base porphyrins and Zn(II) complexes compared to H 2 TPP and ZnTPP, respectively. The first-ring reduction potential of MTPP(NO 2 )MA (1M) exhibited 0.21−0.5 V anodic shift, whereas 0.18− 0.23 V anodic shift was observed in the first-ring oxidation potential compared to the corresponding MTPPs due to the presence of electron-withdrawing β-substituents at the periphery of the macrocycle. Interestingly, NiTPP(NO 2 )MA (1Ni) has shown an additional Ni II /Ni III oxidation potential observed at 2.05 V along with two ring-centered oxidations. The first-ring reduction and oxidation potentials of MTPP(NO 2 )MB (2M) have shown 0.39−0.46 and 0.19−0.27 V anodic shifts with respect to their corresponding MTPPs. The nonlinear optical (NLO) properties of all of the porphyrins were investigated, and the extracted nonlinear optical parameters revealed intense reverse-saturable absorption (RSA) behavior and the self-focusing behavior with positive nonlinear refractive index in the range of (0.19−1.75) × 10 −17 m 2 /W. Zn(II) complexes exhibited the highest two-photon absorption coefficient (β) and cross section (σ TPA ) of ∼95 × 10 −12 m/W and 19.66 × 10 4 GM, respectively, among all of the metal complexes.

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“…30 In 2019, Vijisha et al fabricated fluorinated trans -dicationic pyridinium porphyrins and reported their β and n 2 between 63 and 164 cm GW −1 and 2.27 and 4.49 × 10 −11 esu, respectively at 532 nm, 7 ns, and 10 Hz. 66 In 2018, Shehzad et al utilized tris(alkoxo) ligand Anderson-type polyoxometalates to give β and n 2 in the range of 1.13 to 3.17 × 10 −5 esu and (−) 1.01 to (−) 1.74 × 10 −9 esu respectively at 532 nm, 6 ns, and 10 Hz. 67…”

Section: Resultsmentioning

confidence: 99%

Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis and the spectral, electrochemical, and nonlinear optical properties of β-dicyanovinyl-appended ‘push–pull’ porphyrins

et al. 2022

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Nonlinear optical absorption and refraction properties of fluorinated trans-dicationic pyridinium porphyrin and its metal complexes

Cited by 17 publications

References 46 publications

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

β-Tetracyanobutadiene-Appended Porphyrins: Facile Synthesis, Spectral and Electrochemical Redox Properties, and Their Utilization as Excellent Optical Limiters

Unsymmetrically β-Functionalized π-Extended Porphyrins: Synthesis, Spectral, Electrochemical Redox Properties, and Their Utilization as Efficient Two-Photon Absorbers

Synthesis and the spectral, electrochemical, and nonlinear optical properties of β-dicyanovinyl-appended ‘push–pull’ porphyrins

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