Electron deficient <i>β</i>-trisubstituted porphyrins: synthesis, structural, spectral, and electrochemical studies and their intensity-dependent third-order nonlinear optical properties

A series of electron-deficient <i>β</i>-trisubstituted 12-nitro-5,10,15,20-tetraphenyl-2,3-bis(trifluoromethyl)porphyrins, abbreviated as H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub>, and their metal complexes MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> (where M = Co<sup>II</sup>, Ni<sup>II</sup>, Cu<sup>II</sup>, and Zn<sup>II</sup>) have been prepared and characterised by various spectroscopic techniques. Single crystal X-ray analysis revealed the <i>saddle</i>-shaped configuration of CoTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub>, NiTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> and CuTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> with the average deviation of the 24 core atoms from the mean porphyrin plane (Δ24) ranging from ±0.492 to ±0.499 Å and the average displacement of <i>β</i>-pyrrole carbons from the porphyrin mean plane (ΔC<sub><i>β</i></sub>) ranging from ±0.926 to ±1.005 Å. H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> exhibited a 28 nm red shift in the B-band and a 102 nm red shift in the longest Q-band (Q<sub><i>x</i></sub>(0,0)) as compared to H<sub>2</sub>TPP. In <sup>1</sup>H NMR, the inner imino protons of H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> were observed at -1.72 ppm, which is significantly downfield shifted compared to H<sub>2</sub>TPP. The first ring reduction potential of MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> (M = 2H, Co<sup>II</sup>, Ni<sup>II</sup>, Cu<sup>II</sup>, and Zn<sup>II</sup>) is positively shifted by 280-620 mV compared to their corresponding MTPPs. Notably, it is observed that the synthesized MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> porphyrins are readily reduced compared to their MTPPs. Intensity-dependent third-order nonlinear optical property studies demonstrated that the synthesized asymmetric <i>β</i>-substituted electron-deficient porphyrins exhibit significant two-photon absorption coefficients (<i>β</i> = 0.04-8.10 × 10<sup>-10</sup> m W<sup>-1</sup>) and two-photon absorption cross-section values (<i>σ</i><sub>2PA</sub> = 0.02-1.67 × 10<sup>6</sup> GM). Additionally, the materials exhibit self-defocusing negative nonlinear refraction (<i>n</i><sub>2</sub> = (-) 1.08-40.27 × 10<sup>-17</sup> m<sup>2</sup> W<sup>-1</sup>). The extracted NLO data suggest the potential of the investigated porphyrins for future optoelectronic and advanced material applications.

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Publication Details

Journal
Dalton Transactions
Published
2025-01-01
DOI
https://doi.org/10.1039/d5dt00618j
Citations
3
Primary Topic
Porphyrin and Phthalocyanine Chemistry
Type
article
Field-Weighted Citation Impact
1.55

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article

Electron deficient β-trisubstituted porphyrins: synthesis, structural, spectral, and electrochemical studies and their intensity-dependent third-order nonlinear optical properties

Amritha J. Nair, Muniappan Sankar, Jitendra Nath Acharyya, G. Vijaya Prakash et al.
3 citations
Dalton Transactions
Porphyrin and Phthalocyanine Chemistry
1.55
article

Electron deficient β-trisubstituted porphyrins: synthesis, structural, spectral, and electrochemical studies and their intensity-dependent third-order nonlinear optical properties

Amritha J. Nair, Muniappan Sankar, Jitendra Nath Acharyya, G. Vijaya Prakash, Albin Kuriakose, Reena Jangra
article en
3 citations

Abstract

A series of electron-deficient <i>β</i>-trisubstituted 12-nitro-5,10,15,20-tetraphenyl-2,3-bis(trifluoromethyl)porphyrins, abbreviated as H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub>, and their metal complexes MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> (where M = Co<sup>II</sup>, Ni<sup>II</sup>, Cu<sup>II</sup>, and Zn<sup>II</sup>) have been prepared and characterised by various spectroscopic techniques. Single crystal X-ray analysis revealed the <i>saddle</i>-shaped configuration of CoTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub>, NiTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> and CuTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> with the average deviation of the 24 core atoms from the mean porphyrin plane (Δ24) ranging from ±0.492 to ±0.499 Å and the average displacement of <i>β</i>-pyrrole carbons from the porphyrin mean plane (ΔC<sub><i>β</i></sub>) ranging from ±0.926 to ±1.005 Å. H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> exhibited a 28 nm red shift in the B-band and a 102 nm red shift in the longest Q-band (Q<sub><i>x</i></sub>(0,0)) as compared to H<sub>2</sub>TPP. In <sup>1</sup>H NMR, the inner imino protons of H<sub>2</sub>TPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> were observed at -1.72 ppm, which is significantly downfield shifted compared to H<sub>2</sub>TPP. The first ring reduction potential of MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> (M = 2H, Co<sup>II</sup>, Ni<sup>II</sup>, Cu<sup>II</sup>, and Zn<sup>II</sup>) is positively shifted by 280-620 mV compared to their corresponding MTPPs. Notably, it is observed that the synthesized MTPP(NO<sub>2</sub>)(CF<sub>3</sub>)<sub>2</sub> porphyrins are readily reduced compared to their MTPPs. Intensity-dependent third-order nonlinear optical property studies demonstrated that the synthesized asymmetric <i>β</i>-substituted electron-deficient porphyrins exhibit significant two-photon absorption coefficients (<i>β</i> = 0.04-8.10 × 10<sup>-10</sup> m W<sup>-1</sup>) and two-photon absorption cross-section values (<i>σ</i><sub>2PA</sub> = 0.02-1.67 × 10<sup>6</sup> GM). Additionally, the materials exhibit self-defocusing negative nonlinear refraction (<i>n</i><sub>2</sub> = (-) 1.08-40.27 × 10<sup>-17</sup> m<sup>2</sup> W<sup>-1</sup>). The extracted NLO data suggest the potential of the investigated porphyrins for future optoelectronic and advanced material applications.

Dalton TransactionsVol. 54(26)
Indian Institute of Technology Roorkee (IN), Indian Institute of Technology Delhi (IN)
Department of Science and Technology, Ministry of Science and Technology, India, Science and Engineering Research Board
Openalex Percentile: Top 18%
Porphyrin and Phthalocyanine Chemistry
1.55
DOISourceOpenAlex
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