Dynamic saturable optical nonlinearities in free base tetrapyridylporphyrin

Neto, N.M. Barbosa; Boni, Leonardo De; Rodrigues, José J.; Misoguti, Lino; Mendonça, Cleber Renato; Dinelli, Luís R.; Batista, Alzir A.; Zílio, Sérgio Carlos

doi:10.1142/s1088424603000586

Cited by 29 publications

(5 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…C-H 2 TPyP was synthesized following the procedures described in reference [41], and the spectrometric analysis of the resulting crystals are in good agreement with the literature [42].…”

Section: Methodssupporting

confidence: 61%

Raman Spectroscopy on Free-Base Meso-tetra(4-pyridyl) Porphyrin under Conditions of Low Temperature and High Hydrostatic Pressure

dos Reis,

Leite,

Sharma

et al. 2024

Molecules

View full text Add to dashboard Cite

We present a Raman spectroscopy study of the vibrational properties of free-base meso-tetra(4-pyridyl) porphyrin polycrystals under various temperature and hydrostatic pressure conditions. The combination of experimental results and Density Functional Theory (DFT) calculations allows us to assign most of the observed Raman bands. The modifications in the Raman spectra when excited with 488 nm and 532 nm laser lights indicate that a resonance effect in the Qy band is taking place. The pressure-dependent results show that the resonance conditions change with increasing pressure, probably due to the shift of the electronic transitions. The temperature-dependent results show that the relative intensities of the Raman modes change at low temperatures, while no frequency shifts are observed. The experimental and theoretical analysis presented here suggest that these molecules are well represented by the C2v point symmetry group.

show abstract

“…C-H 2 TPyP was synthesized following the procedures described in reference [41], and the spectrometric analysis of the resulting crystals are in good agreement with the literature [42].…”

Section: Methodssupporting

confidence: 61%

Raman Spectroscopy on Free-Base Meso-tetra(4-pyridyl) Porphyrin under Conditions of Low Temperature and High Hydrostatic Pressure

dos Reis,

Leite,

Sharma

et al. 2024

Molecules

View full text Add to dashboard Cite

show abstract

“…Since complex 1 does not present emission in this spectral range (only a very weak emission at around 540 nm is observed for this complex (Figure 3, SI), and as this new feature is not present in the H 2 TPyP moiety, the observed new spectral signature in the fluorescence spectrum can be attributed to transitions involving states of the two moieties (porphyrin ring and ruthenium outlying group). 44,45 Probably, this new fluorescence peak (around 800 nm) is a deactivation path assigned to charge transfer from ruthenium to porphyrin or vice versa. However, when the sample is excited at the Soret band (425 nm), complex 3a shows similar behavior presented by complex (2), and when excited at 350 and 480 nm, more drastic modifications of fluorescence emission can be observed [see Figure 8(b)].…”

Section: ■ Results and Discussionmentioning

confidence: 93%

“…However, when complex 2 is excited in the region composed by the superposition of intraligand band from the ruthenium groups and at the higher energetic portion of the Soret band (350 nm) and in the region composed by the superposition of MLCT and Q-band (480 nm), a weak, but noticeable new fluorescence feature is observed at around 800 nm [Figure (a)]. Since complex 1 does not present emission in this spectral range (only a very weak emission at around 540 nm is observed for this complex (Figure , SI), and as this new feature is not present in the H 2 TPyP moiety, the observed new spectral signature in the fluorescence spectrum can be attributed to transitions involving states of the two moieties (porphyrin ring and ruthenium outlying group). , …”

Section: Resultsmentioning

confidence: 98%

Remarkable Electronic Effect on the meso-Tetra(thienyl)porphyrins

et al. 2019

Self Cite

View full text Add to dashboard Cite

Complexes derived from meso-tetra(thienyl)porphyrins (TThP) and meso-tetra(pyridyl)porphyrin (TPyP) containing peripheral ruthenium complexes with general formulas {TPyP[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4, {TThP[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4, and {TThP-me-[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4 [5,5′-Mebipy = 5,5′-dimethyl-2,2′-bipyridine and dppb = 1,4-bis(diphenylphosphino)butane] were synthesized and characterized by spectroscopy techniques (1H- and 31P{1H}-NMR, IR, UV/vis, fluorescence, and electron paramagnetic resonance (EPR)), cyclic voltammetry, coulometry, molar conductivity, and elemental analysis. Voltammetry and UV/vis studies demonstrated differentiated electronic properties for ruthenium appended with TThP and TThP-me when compared to ruthenium appended with TPyP. The UV/vis analysis for the ruthenium complex derived from TThP and TThP-me, as well as the Soret and Q bands, characteristics of porphyrins, showed a band at 700 nm referring to the Ru → S electronic transition, and porphyrin TThP-me showed another band at 475 nm from the Ru–N transition. The attribution of these bands was confirmed by spectroelectrochemical analysis. Cyclic voltammetry analysis for the ruthenium complex derived from TPyP exhibited only an electrochemical process with E 1/2 = 0.47 V assigned to the Ru(II)/Ru(III) redox pair (Fc/Fc+). On the other hand, two processes were observed for the ruthenium complexes derived from TThP and TThP-me, with E 1/2 around 0.17 and 0.47 V, which were attributed to the formation of a mixed valence tetranuclear species containing Ru(II) and Ru(III) ions, showing that the peripheral groups are not oxidized at the same potential. Fluorescence spectroscopic experiments show the existence of a mixed state of emission in the supramolecular porphyrin moieties. The results suggest the formation of Ru(II)–Ru(III) mixed valence complexes when oxidation potential was applied around 0.17 V in the {TThP[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4 and {TThP-me-[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4 species.

show abstract

“…Porphyrins 1 , 5 , 8 , and 9 and TPyP as well as NTA derivative 3 were prepared following procedures already reported in the literature. DMF was freshly distilled from MgSO 4 .…”

Section: Methodsmentioning

confidence: 99%

Design and Synthesis of Porphyrin–Nitrilotriacetic Acid Dyads with Potential Applications in Peptide Labeling through Metallochelate Coupling

et al. 2022

View full text Add to dashboard Cite

The need to detect and monitor biomolecules, especially within cells, has led to the emerging growth of fluorescent probes. One of the most commonly used labeling techniques for this purpose is reversible metallochelate coupling via a nitrilotriacetic acid (NTA) moiety. In this study, we focus on the synthesis and characterization of three new porphyrin–NTA dyads, TPP-Lys-NTA, TPP-CC-Lys-NTA, and Py 3 P-Lys-NTA composed of a porphyrin derivative covalently connected with a modified nitrilotriacetic acid chelate ligand (NTA), for possible metallochelate coupling with Ni2+ ions and histidine sequences. Emission spectroscopy studies revealed that all of the probes are able to coordinate with Ni2+ ions and consequently can be applied as fluorophores in protein/peptide labeling applications. Using two different histidine-containing peptides as His6-tag mimic, we demonstrated that the porphyrin–NTA hybrids are able to coordinate efficiently with the peptides through the metallochelate coupling process. Moving one step forward, we examined the ability of these porphyrin–peptide complexes to penetrate and accumulate in cancer cells, exploring the potential utilization of our system as anticancer agents.

show abstract

Dynamic saturable optical nonlinearities in free base tetrapyridylporphyrin

Cited by 29 publications

References 14 publications

Raman Spectroscopy on Free-Base Meso-tetra(4-pyridyl) Porphyrin under Conditions of Low Temperature and High Hydrostatic Pressure

Raman Spectroscopy on Free-Base Meso-tetra(4-pyridyl) Porphyrin under Conditions of Low Temperature and High Hydrostatic Pressure

Remarkable Electronic Effect on the meso-Tetra(thienyl)porphyrins

Design and Synthesis of Porphyrin–Nitrilotriacetic Acid Dyads with Potential Applications in Peptide Labeling through Metallochelate Coupling

Contact Info

Product

Resources

About