Phenylbenzothiazole-Based Platinum(II) and Diplatinum(II) and (III) Complexes with Pyrazolate Groups: Optical Properties and Photocatalysis

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(3), P. 1589 - 1606

Published: Jan. 10, 2024

Based on 2-phenylbenzothiazole (pbt) and 2-(4-dimethylaminophenyl)benzothiazole (Me2N-pbt), mononuclear [Pt(pbt)(R′2-pzH)2]PF6 (R′2-pzH = pzH 1a, 3,5-Me2pzH 1b, 3,5-iPr2pzH 1c) diplatinum (PtII–PtII) [Pt(pbt)(μ-R′2pz)]2 (R′2-pz pz 2a, 3,5-Me2pz 2b, 3,5-iPr2pz 2c) [Pt(Me2N-pbt)(μ-pz)]2 (3a) complexes have been prepared. In the presence of sunlight, 2a 3a evolve, in CHCl3 solution, to form PtIII–PtIII [Pt(R-pbt)(μ-pz)Cl]2 (R H 4a, NMe2 5a). Experimental computational studies reveal negligible influence pyrazole or pyrazolate ligands optical properties 1a–c 2a,b, which exhibit a typical 3IL/3MLCT emission, whereas 2c emission has some 3MMLCT contribution. displays unusual dual, fluorescence (1ILCT 1MLCT/1LC), phosphorescence (3ILCT) emissions depending excitation wavelength. The is lost aerated solutions due sensitization 3O2 formation 1O2, whose determined quantum yield also wavelength dependent. can be reversibly photoinduced (365 nm, ∼ 15 min) oxygenated THF DMSO solutions. 4a 5a, lowest electronic transitions (S1–S3) mixed characters (LMMCT/LXCT/L'XCT LMMCT/LXCT/ILCT 5a) they are weakly emissive rigid media. 1O2 generation property complex successfully used for photooxidation p-bromothioanisol showing its potential application toward photocatalysis.

Language: Английский

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A narrowband red-emitting asymmetric iridium(iii) complex featuring B- and N-embedded π-conjugation units: structure, photophysics and OLED application

Inorganic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 10(4), P. 1262 - 1269

Published: Dec. 24, 2022

A new B- and N-embedded asymmetric iridium complex IrBNacac has been prepared. It exhibited an effective red emission in solid films with a very narrow full width at half maximum (FWHM = 50 nm) finally achieved good OLED device performance.

Language: Английский

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Tuning the Photocatalytic Performance of Ruthenium(II) Polypyridine Complexes Via Ligand Modification for Visible‐Light‐Induced Phosphorylation of Tertiary Aliphatic Amines

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(1)

Published: Oct. 17, 2022

Tuning the redox potential of commonly available photocatalyst to improve catalytic performance or expand its scope for challenging synthetic conversions is an ongoing demand in chemistry. Herein, excited state properties and commercially [Ru(bpy)3 ]2+ were tuned by modifying structure bipyridine ligands with electron-donating/withdrawing units. The visible-light-mediated photoredox phosphorylation tertiary aliphatic amines was demonstrated under mild conditions. A series cross-dehydrogenative coupling reactions performed employing RuII complexes as giving corresponding α-aminophosphinoxides α-aminophosphonates via carbon-phosphorus (C-P) bond formation.

Language: Английский

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Solvent- and Additive-Free Dehydrogenation of N-Heterocycles with Oxygen Catalyzed by Polyoxovanadate-Based Metal–Organic Frameworks

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(49), P. 20228 - 20235

Published: Nov. 21, 2023

N-heteroarenes are a family of organics with significant chemical and pharmaceutical applications. They generally prepared by the catalytic oxidative dehydrogenation (ODH) partially saturated N-heterocycles. In this work, we prepare demonstrate ODH applications two polyoxovanadate-based metal–organic frameworks general formula {[MII(bibp)1.5][VV2O6]}·H2O (M = Ni 1, Co 2; bibp 4,4′-bis(imidazol-1-ylmethyl)biphenyl). based on nonprecious metals, need no additives or organic solvents typically required for ODH, utilize molecular O2 as oxidant, thus possessing all traits desirable practical catalysis. Catalyst 1 shows tolerance range substrates different electronic steric features, including 2,3-dihydro-1H-indole tetrahydroquinolines substituted various functional groups. Mechanistic studies supported primarily evidence from electron paramagnetic resonance X-ray photoelectron spectra suggest that VV sites in catalytically responsible, first enabling formation substrate-based radical species single transfer event while being converted into its mixed-valence form, followed production superoxide anion (O2•–) upon contact O2. The reaction mixture containing O2•– initially formed then undergoes series steps, hydrogen abstraction hydroperoxyl radical, tautomerization dehydrogenated intermediate, finally repeating cycle aforementioned to achieve high-yield conversion corresponding N-heteroarenes.

Language: Английский

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Phenalenyl-Based Photocatalyst for Bioinspired Oxidative Dehydrogenation of N-Heterocycles and Benzyl Alcohols

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4145 - 4155

Published: Feb. 28, 2024

The environmental benefits of molecular oxygen as the oxidizing agent in oxidation reactions that synthesize fine chemicals cannot be overstated. Increased interest developing robust photocatalysts is stimulated by fact current photocatalytic transformation boom has made previously inaccessible synthetic approaches possible. Motivated enzymatic catalysis, employing a reusable phenalenyl-based photocatalyst, we have successfully developed oxidative dehydrogenation utilizing greener oxidant. Under photoinduced conditions, different types saturated N-heterocycles and alcohols were dehydrogenated. versatility this bioinspired protocol demonstrated wide variety N-heteroaromatics, such quinoline, carbazole, quinoxaline, acridine, indole derivatives, well aldehydes ketones, synthesized. Detailed mechanistic studies validate proposed mechanism. Fluorescence lifetime CV experiments revealed crucial role water on efficiency reaction. present also provides chemoselectivity scalability, leading to superior results allowing for functionalization bioactive molecules at late stage sustainable manner.

Language: Английский

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Harnessing photocatalytic activity of mesoporous graphitic carbon nitride decorated by copper single-atom catalysts for oxidative dehydrogenation of N-heterocycles

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 676, P. 485 - 495

Published: July 9, 2024

Language: Английский

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Tailoring the π-system of benzimidazole ligands towards stable light-harvesting cyclometalated iridium(iii) complexes

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(19), P. 6435 - 6450

Published: Jan. 1, 2023

Cyclometalation of 2-arylbenzimidazoles decorated with various polyaromatic fragments leads to formation strongly absorbing iridium dyes applicable in DSSC and enables access structurally diverse iridium( iii ) complexes.

Language: Английский

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Tunable Emissive Ir(III) Benzimidazole‐quinoline Hybrids as Promising Theranostic Lead Compounds

ChemMedChem, Journal Year: 2022, Volume and Issue: 17(18)

Published: June 29, 2022

Bioactive and luminescent cyclometallated Ir(III) complexes [Ir(ppy)2 L1]Cl (1) L2]Cl (2) containing a benzimidazole derivative (L1/L2) as auxiliary mimic of nucleotide have been synthesised. The emissive properties both are conditioned by the nature L1 L2, rendering an orange green emitter respectively. Both highly with quantum yield increasing in absence oxygen up to 0.26 0.36 (2), suggesting their phosphorescent character. Antiproliferative activity against lung cancer A549 cells increased 15 times upon irradiation conditions, reaching IC50 values nanomolar range (0.3±0.09 μM 0.26±0.14 (2)) pointing them good PSs candidates for photodynamic therapy via 1 O2 generation. Cellular biodistribution analysis fluorescence microscopy suggest lysosomes preferential accumulation organelle. Time-resolved studies showed greatly cellular emission lifetime compared solution values, indicating binding macromolecules or structures restriction collision vibrational quenching.

Language: Английский

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A rollover Ir(iii) complex of 2-(6-bromopyridin-2-yl)imidazo[1,2-a]pyridine

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(12), P. 5625 - 5633

Published: Jan. 1, 2023

Rollover iridacycle were easily obtained via a C–H bond activation on the remote position of 2-(6-bromopyridin-2-yl)imidazo[1,2- ]pyridine ligand. DFT calculations suggest that occurs during complexation second

Language: Английский

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In Situ Probing the Short-Lived Intermediates in Visible-Light Heterogeneous Photocatalysis by Mass Spectrometry

Analytical Chemistry, Journal Year: 2023, Volume and Issue: 95(37), P. 14150 - 14157

Published: Sept. 4, 2023

Visible-light-mediated heterogeneous photocatalysis has recently emerged as an environmentally friendly and energy-sustainable alternative for organic transformations. Despite the advancements in developing wide varieties of photocatalysts during past decades, accurate probing identification photogenerated species, especially short-lived radical intermediates, are still challenging. In this work, we reported a hybrid ion emitter that integrated with pico-liter photocatalytic reactor, which was fabricated by depositing photocatalyst (e.g., TiO2) into front tip quartz micropipette. Benefited from dual-function feature micropipette (i.e., clog-free tip-confined reactor nanoelectrospray ionization), sensitized photoredox reactions at catalyst-solution interface can be triggered upon visible-light irradiation using cheap LED laser (453 nm), newly produced transient intermediates rapidly transformed gaseous ions mass spectrometric identification. Using novel low-delay coupling device, including cationic radicals photooxidation anilines anionic photoreduction quinones, were successfully captured spectrometry. We believe our photochemical microreactor/ion provided new powerful tool exploring complicated processes, their ultrafast initial

Language: Английский

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