Synthesis of 2-nitro-3-(pyrrol-1-yl)-5,10,15,20-tetraarylporphyrins via a Clauson-Kaas reaction and the study of their electronic properties

Tiwari, Raju; Nath, Mahendra

doi:10.1039/c5nj00014a

Cited by 15 publications

(7 citation statements)

References 39 publications

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“…Since both Soret and Q bands arise from → * transitions, they can be explained by the Gouterman four orbital model (frontier HOMO and LUMO orbitals) [51,52]. The red shift of these bands indicates πconjugation increasing and a HOMO-LUMO energy gap reduction [53][54][55] caused by the molecules symmetry increasing. The change in the symmetry from D2h in free base porphyrin to D4h in the metalloporphyrin leads only to two absorptions of Q (0,0) and Q (1,0) and a red shift.…”

Section: Photophysical Propertiesmentioning

confidence: 99%

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

et al. 2018

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Chemical preparation, X-ray diffraction, spectral and photophysical studies were performed for H 2 TPBP (5,10,15,20-tetrakis[4 (benzoyloxy)phenyl] porphyrin), [Mg(TPBP)], and the [Mg II (TPBP)(4,4'-bpy) 2 ] (I) complex (4,4'-bpy = 4,4'-bipyridine). This study shows a 1D coordination polymer chain of alternating [Mg II (TPBP)] and 4,4′-bipyridine molecule located at the axial position of the magnesium(II) coordination sphere. The magnesium ion is coordinated to four nitrogen atoms from the porphyrin ring and two nitrogen atoms from the axial ligands, forming a regular octahedron. The crystal packing and the linear coordination chains for this complex are stabilized by weak inter and intramolecular interactions involving centroids (Cg) porphyrin pyrrole and the pyridyl group of the 4,4'-bipyridine rings. Infrared (IR), proton nuclear magnetic resonance ( 1 H NMR) spectroscopies, mass spectroscopy, and elemental analysis were also investigated to confirm the crystal structure. UV-Visible absorption spectrum of complex I displayed a red shifted Soret (430 nm) and Q (571 and 614 nm) bands due to the extended conjugation. However, fluorescence emission spectrum shows larger blue shift of ~ 41 and ~ 54 nm for Q (0,0) and Q (0.1), respectively.

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Section: Photophysical Propertiesmentioning

confidence: 99%

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

et al. 2018

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“…Both P 1 and P 2 – P 4 exhibit two characteristic S 1 emissions, i.e., Q(0,0) and Q(0,1) at 656 and 720 nm followed by a less common S 2 emission, i.e., B(0,0) at 421 nm. The appearance of the B(0,0) band in addition to Q(0,0) and Q(0,1) bands signifies an appreciable mirror-image relationship between the corresponding absorption and photoluminescence emission bands of P 1 – P 4 . The smaller Stokes shift between the S 0 –S 2 excitation and S 0 –S 2 emission (∼3 nm) in P 1 – P 4 further suggests that the molecules do not undergo much change in their geometries upon exciting from ground states to the electronically excited states .…”

Section: Results and Discussionmentioning

confidence: 97%

“…The appearance of the B(0,0) band in addition to Q(0,0) and Q(0,1) bands signifies an appreciable mirror-image relationship between the corresponding absorption and photoluminescence emission bands of P 1 −P 4 . 21 The smaller Stokes shift between the S 0 −S 2 excitation and S 0 −S 2 emission (∼3 nm) in P 1 −P 4 further suggests that the molecules not undergo much change in their geometries upon exciting from ground states to the electronically excited states. 22 It is clear from Figure 9 that the emission intensities corresponding to P 2 −P 4 are higher relative to P 1 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Preparations of Core H₂O-Bound 5, 10, 15, 20-Tetrakis-4-chlorophenyl Porphyrin, P₁, and O-Methylation of Phenol and Its P-Substituted Analogues

Dechan

Bajju

2020

ACS Omega

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The treatment of a dichloromethane solution of 5, 10, 15, 20-tetrakis-4-chlorophenyl porphyrin, P 1 , with methanolic solutions of each of phenol, p -amino phenol, and p -nitro phenol for just 1 h results in the formation of water-molecule-bound amorphous solids of P 1 . In addition to the straightforward access to the H 2 O-molecule-coordinated species of P 1 thus produced, the another chief advantage of this synthetic strategy is the successful recoveries of anisole, p -amino anisole, and p -nitro anisole at the end of the reactions. The present work therefore further reports the use of P 1 as an efficient catalyst for the selective O -methylation of phenols using methanol as an environmentally friendly methylating agent. The H 2 O-bound amorphous solids of P 1 exhibit higher-intensity absorption as well as photoluminescence emission bands in dichloromethane compared with the parent crystalline form. Further, the measurement of the solid-state emission properties of both the crystalline and amorphous forms indicates quenching of fluorescence bands corresponding to amorphous solids in comparison with that of parent crystalline form. The crystalline form of P 1 and the H 2 O-bound amorphous solids were further studied by scanning electron microscope/transmission electron microscope (SEM/TEM), powder X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and thermal analysis techniques. The results of these studies indicate change in morphological and structural features, surface areas, porosities, and thermal robustness upon core coordination of water molecules with the macrocyclic rings of P 1 .

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“…where E ele , E pol , E dis and E rep represent electrostatic, polarization, dispersion, and repulsive energies, respectively [29].…”

Section: Non-covalent-interactions (Nci) and Hirshfeld Surface For In...mentioning

confidence: 99%

Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound

et al. 2022

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This study describes the synthesis, theoretical investigations, and photocatalytic degradational properties of a new (pyrazine)(meso-tetrakis(4-tert-methoxyphenyl)-porphyrinato)-cadmium (II) ([Cd(TMPP)-Pyz] complex (1). The new penta-coordinated CdII porphyrin complex (1) was characterized by various spectroscopic techniques, including FT-IR, NMR, UV-visible absorption, fluorescence emission, and singlet oxygen, while its molecular structure was studied using single crystal X-ray diffraction. The UV–Vis spectroscopic study highlighted the redshift of the absorption bands after the insertion of the Cd(II) metal ion into the TMPP ring. The co-coordination of the pyrazine axial ligand enhanced this effect. A fluorescence emission spectroscopic study showed a significant blueshift in the Q bands, accompanied by a decrease in the fluorescence emission intensity and quantum yields of Φf = 0.084, Φf = 0.06 and Φf = 0.03 for H2-TMPP free-base porphyrin, [Cd(TMPP)] and [Cd(TMPP)(Pyz)] (1) respectively. Singlet oxygen revealed that the H2-TMPP porphyrin produced the most efficient singlet oxygen quantum yield of (ΦΔ = 0.73) compared to [CdTMPP] (ΦΔ = 0.57) and [Cd(TMPP)(Pyz)] (1) (ΦΔ = 0.13). In the crystal lattice, the [Cd(TMPP)Pyz]) was stabilized through non-covalent intermolecular interactions (NCI), such as the hydrogen bonds C-H···N and C-H···Cg. Additionally, crystal explorer software was then utilized to measure the quantitative analysis of the intermolecular interactions in the unit cell of the crystal structure and established that the C-H···π interaction dominated. The Natural bond orbital (NBO) analysis revealed that each molecule is stabilized by hyperconjugation and charge delocalization. As a photocatalyst, the coordination complex 1 showed excellent photocatalytic activity toward the degradation of Levafix Blue CA reactive dye (i.e., dye photo-degradation of 80%).

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Synthesis of 2-nitro-3-(pyrrol-1-yl)-5,10,15,20-tetraarylporphyrins via a Clauson-Kaas reaction and the study of their electronic properties

Abstract: Versatile synthesis of new porphyrin building blocks, 2-nitro-3-(pyrrol-1-yl)-5,10,15,20-tetraarylporphyrins is described. These porphyrins demonstrate red shifted absorption bands and S2 emission.

Cited by 15 publications

References 39 publications

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

Preparations of Core H₂O-Bound 5, 10, 15, 20-Tetrakis-4-chlorophenyl Porphyrin, P₁, and O-Methylation of Phenol and Its P-Substituted Analogues

Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound

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Synthesis of 2-nitro-3-(pyrrol-1-yl)-5,10,15,20-tetraarylporphyrins via a Clauson-Kaas reaction and the study of their electronic properties

Abstract: Versatile synthesis of new porphyrin building blocks, 2-nitro-3-(pyrrol-1-yl)-5,10,15,20-tetraarylporphyrins is described. These porphyrins demonstrate red shifted absorption bands and S2 emission.

Cited by 15 publications

References 39 publications

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

Synthesis, molecular structure, photophysical properties and spectroscopic characterization of new 1D-magnesium(II) porphyrin-based coordination polymer

Preparations of Core H2O-Bound 5, 10, 15, 20-Tetrakis-4-chlorophenyl Porphyrin, P1, and O-Methylation of Phenol and Its P-Substituted Analogues

Synthesis, Characterization, DFT and Photocatalytic Studies of a New Pyrazine Cadmium(II) Tetrakis(4-methoxy-phenyl)-porphyrin Compound

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Preparations of Core H₂O-Bound 5, 10, 15, 20-Tetrakis-4-chlorophenyl Porphyrin, P₁, and O-Methylation of Phenol and Its P-Substituted Analogues