Meso-β, β-β’ Trifused Porphyrins: Synthesis, Spectral, Electrochemical and DFT Studies and Their Femtosecond Third-Order Nonlinear Optical Properties

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Meso -β, β–β′ trifused porphyrins have been synthesized and exhibited nonplanar conformation with a high dipole moment values. Femtosecond third-order NLO measurements demonstrated promising 3PA coefficients cross-section

Language: Английский

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Enhanced Catalytic Activity of Binuclear Oxidovanadium(IV) Bisbenzimidazole Linked Porphyrin Dimer for the Generation of Biologically Active 3,4-Dihydropyrimidinones and Their Corresponding Thiones

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(24), P. 11102 - 11112

Published: June 4, 2024

Binuclear vanadyl(IV) porphyrin (V2BP), where two vanadium(IV) macrocycles are linked through benzimidazole units at the β-positions, has been prepared and characterized with various techniques, such as UV–vis, Fourier transform-infrared, electron paramagnetic resonance, cyclic voltammetry, density functional transform calculations, mass spectrometry. V2BP exhibits a red shift (Δλmax = 10 nm) in Soret band compared unsubstituted parent meso-tetraphenylporphyrin (VP). The synthesized binuclear (V2BP) further studied catalyst to explore single-pot multicomponent Biginelli reaction producing biologically active 3,4-dihydropyrimidin-2-(1H)-one (DHPM)-based biomolecules corresponding thiones under solvent-free conditions its catalytic activity Several conditions, amount of catalyst, time, solvent, temperature, have optimized obtain maximum yield DHPMs or thiones. β-functionalized dimer manifests much higher conversion (84–95% yield) high TON (4454–5037) TOF (1113–1259 h–1) values for one-pot literature. exhibited excellent recyclability up cycles.

Language: Английский

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Nonlinear optical properties of bandwidth-controlled reflective PSLC films prepared by electrospinning

Applied Materials Today, Journal Year: 2025, Volume and Issue: 43, P. 102678 - 102678

Published: March 11, 2025

Language: Английский

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Effect of para‐Substituents on meso‐Functionalized Oxidovanadium(IV) Porphyrins as Catalysts for Oxygen Atom Transfer Mediated Oxidation of Benzoin to Benzil under Mild Conditions

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(30)

Published: July 31, 2023

Abstract Systematic analysis of the effect para ‐substituents (H, Cl, Br and OMe) on meso ‐phenyl group in vanadyl ‐tetraphenylporphyrins ([V IV O(TPP)] (R=H, 1 ), [V O(TCPP)] (R=Cl, 2 [ V O(TBPP)] (R=Br, 3 ) O(TMPP)] (R=OMe, 4 )) their properties catalytic oxygen atom transfer (OAT) for oxidation benzoin to benzil using DMSO as well 30 % aqueous H O sacrificial source have been studied. Electrochemical theoretical (density functional theory) studies are good agreement with influence these substituents property complexes. Complex ( displayed best activity conversion (92 %) h >99 product selectivity when was used an source, whereas excellent (~100 noticed 18 95 a oxygen. Furthermore, among complexes, electron‐withdrawing nature chloro substituent at p ‐position significantly influences transfer. Experimental simulated EPR confirmed +4 vanadium The structure , by single crystal X‐ray diffraction method, domed shape, displacement V(IV) ion from mean porphyrin plane follows order: (0.458 Å) < (0.459 (0.479 Å). We observed that dimethyl sulfide much.

Language: Английский

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Structurally influenced optical nonlinearities and ultrafast dynamics in β-acroleyl- and β-dicyanobutadienyl-appended cobalt corroles

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(21), P. 15125 - 15129

Published: Jan. 1, 2024

The strong two-photon induced nonlinear absorption and self-focusing type positive refraction are pronounced by the structural engineering in β-functionalized cobalt corroles.

Language: Английский

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Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(49), P. 19956 - 19970

Published: Nov. 27, 2023

Four new β-functionalized π-extended cobalt corroles with one and two dicyanovinyl (DCV) or dicyanobutadienyl (DCBD) moieties at the 3- 3,17-positions have been synthesized characterized by various spectroscopic techniques. Interestingly, DCV- DCBD-appended displayed panchromatic near-infrared absorption in range 300–1100 nm CH2Cl2 pyridine solvents. (MN)2-(Cor)Co A2MN2-(Cor)Co exhibited 8–9 times enhancement molar absorptivity of Q band compared to parent corrole ((Cor)Co). The unique spectral features these are splitting, broadening, red-shifting Soret bands. One DCV unit brings a 30–46 red shift, whereas DCBD 40–75 shift corresponding precursors. This is rare that intensity longest greater than equal Soret-like These derivatives exhibit UV–vis similar those chlorophyll a. A 220 mV positive per group 160 were observed first oxidation potentials (Cor)Co desired direction for utility complexes electrocatalysis. DFT studies revealed HOMO LUMO stabilized after appending groups on macrocycle “push–pull” behavior leading promising material applications nonlinear optics (NLO) catalysis.

Language: Английский

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Synthesis, Structural, Electrochemical, and DFT Studies of Highly Substituted Nonplanar Ni(II) Porphyrins and Their Intensity-Dependent Third-Order Nonlinear Optical Properties

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

We designed and successfully synthesized highly substituted electron-deficient nonplanar Ni(II) porphyrins their derivatives (

Language: Английский

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Single Pyrrole Unit Functionalized Electron Deficient Porphyrins and Their Metal Complexes: Synthesis, Structural, Spectral and Electrochemical Properties

ChemistrySelect, Journal Year: 2023, Volume and Issue: 8(48)

Published: Dec. 19, 2023

Abstract A family of electron‐deficient regioselective β ‐disubstituted meso ‐tetraphenylporphyrins, H 2 TPP(R) (where R=trifluoromethyl (CF 3 ) and cyano (CN) its metal complexes (Co(II), Ni(II), Cu(II) Zn(II)) were synthesized from versatile precursor TPPBr by palladium‐catalyzed trifluoromethylation nucleophilic aromatic cyanation respectively. The absorption spectrum TPP(CF TPP(CN) exhibited a notable shift towards longer wavelengths both in the Soret (Δλ ma x =16–17 nm) longest wavelength band, Q (0,0) max =34–52 as compared to porphyrin, . first ring reduction potential are centred at −0.69 −0.68 respectively which show drastic anodic (−1.01 V) parent porphyrin TPP (−1.25 V). trend for potentials follows >H >H2TPP(Br) TPP. Introducing two highly electron withdrawing substituents (CN CF single pyrrole unit macrocycle via substitution has led significant HOMO‐LUMO energy gap (0.15 V–0.39 comparison (2.08 analysis crystal structures ZnTPP(CN) revealed nearly planar distinct saddle conformations further supported DFT calculations.

Language: Английский

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Structural, photophysical, and electrochemical redox properties of meso-tetrakis(pentafluorophenyl)porphyrins

Journal of Porphyrins and Phthalocyanines, Journal Year: 2024, Volume and Issue: 28(02), P. 97 - 106

Published: Jan. 29, 2024

This study delineates the synthesis and comprehensive characterization of metal complexes meso-tetrakis(pentafluorophenyl)porphyrin (H 2 TPF[Formula: see text]P, 1) with first-row transition ions (M = Mn(III) 2, Fe(III) 3, Co(II) 4, Ni(II) 5, Cu(II) 6, Zn(II) 7) to elucidate their structural, electronic spectral, electrochemical redox properties. Co, Ni, Cu Zn Complexes exhibit planar structure ([Formula: text]24 0.003-0.021 Å [Formula: text]C[Formula: text] 0.004−0.041 Å) which is also confirmed by single crystal data complex ZnTPF[Formula: 7 shows geometry, while Fe Mn show slightly nonplanar 0.101–0.143 0.080–0.112 Å), are distorted due occupied axial sites −Cl ligand as revealed density functional theory (DFT) calculations. Furthermore, spectroscopy a gradual bathochromic shift following order NiTPF[Formula: text]P < CoTPF[Formula: CuTPF[Formula: text]PCl H FeTPF[Formula: MnTPF[Formula: appending different in porphyrin core. exhibited most significant 63 nm) Soret band compared text]P. Also, unique pattern split at around 364 345 nm interaction between text]-orbitals surrounding ligands. The potentials filled 3d orbital endow (ring centered) lowest oxidation potential.

Language: Английский

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The synthesis of highly nonplanar oxidovanadium(IV) porphyrins as robust catalysts for oxidative bromination of phenols in aqueous medium

Journal of Porphyrins and Phthalocyanines, Journal Year: 2024, Volume and Issue: 28(04), P. 225 - 235

Published: April 1, 2024

Two new complexes, oxidovanadium(IV) 2,3,5,10,12,13,15,20-octaphenyl-7,8,17,18-tetrabromoporphyrin V(IV)O(OPP)Br 4 (2), and 2,3,5,10,12,13,15,20-octaphenyl-7,8,17,18-tetrachloroporphyrin V(IV)O(OPP)Cl (3) starting from 2,3,5,10,12,13,15,20-octaphenylporphyrin V(IV)O(OPP) (1) have been prepared in good yields characterized by various spectroscopic techniques. The single-crystal DFT-optimized structures of these porphyrins showed a highly nonplanar saddle-shape conformation the porphyrin macrocycle. In cyclic voltammograms, first ring oxidation potential reduction (2) anodic shift as compared to (1), indicating electron-deficient nature both porphyrins. state vanadium synthesized complexes +4 was confirmed EPR spectroscopy, exhibited axially compressed [Formula: see text] configuration. These were utilized catalysts for oxidative bromination thymol other phenol derivatives with excellent conversion ([Formula: 99.9%), selectivity, high TOF value (86869 h[Formula: text].

Language: Английский

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