Spectral, Electrochemical, and Photochemical Characterization of Donor-Acceptor Supramolecular Systems DOI

Anuradha Liyanage

Published: July 1, 2023

This dissertation research work focuses on the investigation of novel donor-acceptor systems elucidating their photochemical properties, anion binding, and potential application in development artificial photosynthetic systems. The explored are based oxoporphyrinogen (OxPs), porphyrins, fullerene, boron dipyrromethene (BODIPY) properties molecular were elucidated using UV-vis spectroscopy, fluorescence electrochemical methods, computational calculations, ultrafast transient absorption spectroscopy. A BODIPY-oxoporphyrinogen dyad which is able to bind with fluoride promoting excited state electron energy transfer events mimicking primary natural photosynthesis was introduced. Further, self-assembly supramolecular complexes oxoporphyrinogens, different zinc porphyrin dimers explored. formed self-assembled have shown photoinduced transfer. push-pull construct spiro-locked N-heterocycle-fused studied. charge separation stabilization this system enhanced by complexation anion. Also, effect BODIPY functionalization linkers a series carbazole–BODIPY phenothiazine-BODIPY dyads investigated. These findings important develop advanced efficient BODIPY-based for light harvesting applications. entire study aims expand our understanding these contribute towards advancement sustainable technologies.

Language: Английский

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

Jhansi Mogilipuri,

S. Venugopal Rao

et al.

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

Citations

1
Photophysics of corroles and closely related systems for emergent solar energy, medicinal, and materials science applications DOI
Xuan Zhan, Donghyeon Kim, Zakir Ullah

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 495, P. 215363 - 215363

Published: Aug. 22, 2023

Language: Английский

Citations

20
Oxido-Molybdenum(V) Corroles as Robust Catalysts for Oxidative Bromination and Selective Epoxidation Reactions in Aqueous Media under Mild Conditions DOI
Inderpal Yadav, Ved Prakash, Mannar R. Maurya

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(13), P. 5292 - 5301

Published: March 23, 2023

Two new meso-substituted oxido-molybdenum corroles were synthesized and characterized by various spectroscopic techniques. In the thermogram, MoO[TTC] (1) exhibited excellent thermal stability up to 491 °C while MoO[TNPC] (2) good 318 °C. The oxidation states of molybdenum(V) verified electron paramagnetic resonance (EPR) spectroscopy an axial compression with dxy1 configuration. Oxido-molybdenum(V) complexes utilized for selective epoxidation olefins high TOF values (2066-3287 h-1) in yields a CH3CN/H2O (3:2, v/v) mixture presence hydrogen peroxide as green oxidant NaHCO3 promoter. oxidative bromination catalytic activity oxido-molybdenum(V) aqueous medium has been reported first time. Surprisingly, biomimics vanadium bromoperoxidase (VBPO) enzyme remarkably (36 988-61 646 p-cresol other phenol derivatives. Catalyst higher better than catalyst due electron-withdrawing nitro groups evident from cyclic voltammetric studies.

Language: Английский

Citations

19
Symmetrically Functionalized Copper and Silver Corrole‐Bis‐Tetracyanobutadiene Push‐Pull Conjugates: Efficient Population of Triplet States via Charge Transfer DOI Creative Commons
Inderpal Yadav, Jatan K. Sharma, Muniappan Sankar

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(41)

Published: May 3, 2023

Copper and silver tritolylcorroles (TTC) are symmetrically functionalized to carry two tetracyanobutadiene (TCBD) entities via [2+2] cycloaddition-retroeletrocyclization reaction involving ethynyl corroles with an electron acceptor, tetracyanoethylene (TCNE) in excellent yields, as the first examples of corrole-TCBD push-pull systems. The strong effect resulted charge polarization ground state resulting a considerable hypsochromic shift spectrum extending it into near-IR region. Electrochemical studies coupled computational revealed interactions between TCBD corrole π-system degree such was found depend on metal ion present cavity. Energy considerations suggested transfer (CT) from S2 or vibrationally hot S1 but not relaxed case CuTTC(TCBD)2 while CT occur all these states AgTTC(TCBD)2 . Additionally, high-energy populate low-lying triplet states. Systematic femtosecond pump-probe provided ultimate proof for occurrence excited function excitation wavelength followed by efficient population study brings out significance efficiently populating rather unusual copper carrying entities.

Language: Английский

Citations

11
Push–pull octaphenylporphyrins with mixed substituents pattern: Synthesis, redox, ultrafast dynamics and nonlinear optical studies DOI

Soni Kumari,

Inderpal Yadav, Jitendra Nath Acharyya

et al.

Dyes and Pigments, Journal Year: 2023, Volume and Issue: 217, P. 111416 - 111416

Published: May 17, 2023

Language: Английский

Citations

11
Synthesis, Spectral, Redox, and Sensing Studies of β-Dicyanovinyl-Appended Corroles and Their Metal Complexes DOI
Inderpal Yadav, W. Ryan Osterloh, Karl M. Kadish

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(20), P. 7738 - 7752

Published: May 5, 2023

A new family of β-dicyanovinyl (DCV)-appended corroles represented as MTPC(MN) (where M = 3H, Cu, Ag, and Co(PPh3) MN malononitrile TPC 5,10,15-triphenylcorrole) were synthesized starting from the free base mono β-formyl corrole, H3TPC(CHO), characterized along with their respective MTPC(CHO) MTPC complexes to spectroscopic electrochemical properties in nonaqueous media. Comparisons between two series demonstrate a pronounced substituent effect β-DCV group on physicochemical making derivatives substantially easier reduce more difficult oxidize than formyl or unsubstituted corroles. In addition, colorimetric spectral detection 11 different anions (X) form tetrabutylammonium salts (TBAX, X PF6-, OAc-, H2PO4-, CN-, HSO4-, NO3-, ClO4-, F-, Cl-, Br-, I-) also investigated Of anions, only CN- was found induce changes UV-vis 1H NMR spectra metallocorroles. This data revealed that CuTPC(MN) AgTPC(MN) act chemodosimeters for selective cyanide ion via nucleophilic attack at vinylic carbon DCV substituent, while (PPh3)CoTPC(MN) acts chemosensor sensing axial coordination cobalt metal center. low-limit ions observed 1.69 ppm 1.17 toluene.

Language: Английский

Citations

10
Single- and two-photon absorption properties of gallium corroles DOI
Lili Wang,

Shi-Ye Huang,

Bei Wan

et al.

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1303, P. 137564 - 137564

Published: Jan. 12, 2024

Language: Английский

Citations

3
Structurally influenced optical nonlinearities and ultrafast dynamics in β-acroleyl- and β-dicyanobutadienyl-appended cobalt corroles DOI
Inderpal Yadav, Jitendra Nath Acharyya, G. Vijaya Prakash

et al.

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

Citations

2
Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature DOI
Inderpal Yadav, Ved Prakash,

Ram R. Kaswan

et al.

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(34)

Published: Sept. 19, 2023

Abstract Two new β ‐functionalized oxidomolybdenum(V) corroles, oxido[3‐formyl‐5,10,15‐triphenylcorrolato]molybdenum(V) ( Mo‐1 ) and oxido[3‐dicyanovinyl‐5,10,15‐triphenylcorrolato]molybdenum(V) Mo‐2 were synthesized characterized by various spectroscopic techniques electrochemical studies. manifests splitted B bands due to x y polarizations highly red shifted longest Q the electron‐deficient nature of dicyanovinyl group. EPR data showed that these complexes exhibit an axial compression with d xy 1 configuration. DFT studies revealed HOMO LUMO orbitals are stabilized in relative . exhibits two successive reversible reductions oxidation potentials cyclic voltammetry. Surprisingly, three oxidations; one extra reduction could possibly be moiety. The catalytic activities for oxidative bromination phenols using H 2 O ‐KBr‐HClO 4 mixture water have been explored exhibited excellent activity at a very low catalyst loading 0.0030 0.0028 mol%, respectively. Both Mo(V) corroles manifest much higher conversion TOF (59801–71174 h −1 earlier reported meso (20781–61646 ). Hence, mimic vanadium bromoperoxidase (VBPO) act as functional models applications. These catalysts reused upto 3 cycles rate 82 % indicating their thermal chemical stabilities.

Language: Английский

Citations

6
Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles DOI
Inderpal Yadav, Muniappan Sankar

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

Citations

5