Flexible Linker-Based Triazine-Functionalized 2D Covalent Organic Frameworks for Supercapacitor and Gas Sorption Applications

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(9), P. 11605 - 11616

Published: Feb. 26, 2024

Covalent organic frameworks (COFs) having a large surface area, porosity, and substantial amounts of heteroatom content are recognized as the ideal class materials for energy storage gas sorption applications. In this work, we have synthesized four different porous COF by polycondensation heteroatom-rich flexible triazine-based trialdehyde linker, namely 2,4,6-tris(4-formylphenoxy)-1,3,5-triazine (TPT-CHO), with triamine linkers. Triamine linkers were chosen based on differences in size, symmetry, planarity, content, leading to synthesis named IITR-COF-1, IITR-COF-2, IITR-COF-3, IITR-COF-4. within 24 h from most planar largest amine monomer, exhibited Brunauer-Emmett-Teller (BET) area 2830 m

Language: Английский

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Mono- and bis-Pd(ii) complexes of N-confused dithiahexaphyrin(1.1.1.1.1.0) with the absorption and aromaticity modulated by Pd(ii) coordination, macrocycle contraction and ancillary ligands

Chemical Science, Journal Year: 2024, Volume and Issue: 15(6), P. 2047 - 2054

Published: Jan. 1, 2024

From a single N-confused dithiahexaphyrin ligand, five mono- and bis-Pd( ii ) complexes have been synthesized, the absorption aromaticity can be modulated by Pd( coordination, macrocycle contraction ancillary ligands.

Language: Английский

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Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 125 - 154

Published: Jan. 22, 2024

Various push–pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition–retroelectrocyclization (CA–RE) reactions involving diverse electron-rich alkynes electron-deficient alkenes. In this review, comprehensive investigation of the recent noteworthy advancements research on prepared via CA–RE reaction is conducted. particular, an overview physicochemical properties family these compounds that have been investigated provided to clarify their potential for future applications.

Language: Английский

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Synthesis of Nonplanar Push–Pull Chromophores with Various Heterocyclic Moieties via [2 + 2] Cycloaddition-Retroelectrocyclization Reaction

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

A series of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives with various heterocyclic moieties, including pyridine, carbazole, indole, and benzothiadiazole, was newly synthesized through a [2 + 2] cycloaddition-retroelectrocyclization reaction. Symmetric electron-rich 1,3-butadiynes end-capped substituents were reacted tetracyanoethylene (TCNE), yielding the target TCBD products in 60–80% yields under ambient or mild heating conditions. The thermal stability optical electrochemical properties both 1,3-butadiyne precursors corresponding investigated by using thermogravimetric analysis (TGA), UV–vis spectroscopy, cyclic voltammetry (CV). featured narrow bandgaps due to intramolecular charge transfer interactions push–pull chromophores. In addition, optimized structures frontier molecular orbitals their energy levels determined density functional theory (DFT) calculations.

Language: Английский

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Acceptor-Dependent Intervalence Charge Transfer and Separation Dynamics in Broad-Band-Capturing Push–Pull Chromophores

The Journal of Physical Chemistry C, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

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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Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

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

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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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Novel Benzothiadiazole‐based Donor‐Acceptor Systems: Synthesis, Ultrafast Charge Transfer and Separation Dynamics

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 23, 2024

Abstract Near‐infrared (NIR) absorbing electron donor‐acceptor (D−A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we designed and developed a new set benzothiadiazole (BTD)‐based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)‐embedded multimodular D−A systems ( BTD1‐BTD6 ) investigated inherent photo‐electro‐chemical responses first time having identical mixed terminal donors variable donicity. Apart from poor luminescence, appearance broad low‐lying optical transitions extendable even in NIR region (>1000 nm), particularly presence auxiliary acceptors, indicative underlying nonradiative excited state processes leading robust intramolecular CT subsequent separation (CS) these constructs. While electrochemical studies identify moieties involved photo‐events, orbital delocalization consequent evidence low‐energy achieved theoretical calculations. Finally, spectral temporal different photoproducts obtained femtosecond transient absorption studies, which, coupled with spectroelectrochemical data, signals as CS states compounds. All found be susceptible ultrafast (~ps) before carrier recombination ground state, is, however, significantly facilitated after incorporation secondary TCBD/DCNQ faster thus efficient processes, polar solvents. These findings, including CT/CS intense panchromatic over wide window electromagnetic spectrum, likely expand horizons BTD‐based revolutionize realm solar conversion associated photonic

Language: Английский

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Zinc Tetrapyrrole Coordinated to Imidazole Functionalized Tetracyanobutadiene or Cyclohexa‐2,5‐diene‐1,4‐diylidene‐expanded‐tetracyanobutadiene Conjugates: Dark vs. Light‐Induced Electron Transfer

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(68)

Published: Sept. 14, 2023

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors imidazole functionalized tetracyanobutadiene (Im-TCBD) cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) acceptors. The newly formed were fully characterized by a suite of physicochemical methods, including absorption emission, electrochemistry, computational methods. measured binding constants for 1 : complexes in order 104 -105 M-1 o-dichlorobenzene. Free-energy calculations energy level diagrams revealed high exergonicity excited state transfer reactions. However, case ZnNc:Im-DCNQ complex, owing to facile oxidation ZnNc reduction Im-DCNQ, slow was witnessed dark without aid light. Systematic transient pump-probe studies performed secure evidence charge separation gather their kinetic parameters. rate 1011 s-1 suggesting efficient processes. These findings show that present approach could be utilized build constructs with powerful acceptors, TCBD DCNQ, witness ground transfer, fundamental events required harvesting, building optoelectronic devices.

Language: Английский

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