Dataset Information

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

ABSTRACT: Red-emissive ?-expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching ?=750?nm can be easily synthesized by a three-step strategy involving the preparation of diketopyrrolopyrrole followed by N-arylation and subsequent intramolecular palladium-catalyzed direct arylation. Comprehensive spectroscopic assays combined with first-principles calculations corroborated that both N-arylated and fused DPPs reach a locally excited (S₁ ) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6?% to 88?% in nonpolar solvents and from 0.4?% and 3.2?% in polar solvents. A very inefficient (T₁ ) population is responsible for fluorescence quantum yields as high as 88?% for the fully fused DPP in polar solvents.

SUBMITTER: Skonieczny K

PROVIDER: S-EPMC7689858 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

Skonieczny Kamil K Papadopoulos Ilias I Papadopoulos Ilias I Thiel Dominik D Gutkowski Krzysztof K Haines Philipp P McCosker Patrick M PM Laurent Adèle D AD Keller Paul A PA Clark Timothy T Jacquemin Denis D Guldi Dirk M DM Gryko Daniel T DT

Angewandte Chemie (International ed. in English) 20200710 37

Red-emissive π-expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three-step strategy involving the preparation of diketopyrrolopyrrole followed by N-arylation and subsequent intramolecular palladium-catalyzed direct arylation. Comprehensive spectroscopic assays combined with first-principles calculations corroborated that both N-arylated and fused DPPs reach a locally excited (S<sub>1</sub> ) state after excitation, followed by internal conv ...[more]

PMID: 32492240

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Project description:The analytical capabilities associated with the use of silylation reactions have been extended to a new class of organic molecules, nitroaromatic compounds (NACs). These compounds are a possible contributor to urban particulate matter of secondary origin which would make them important analytes due to their (1) detrimental health effects, (2) potential to affect aerosol optical properties, and (3) and usefulness for identifying PM2.5 from biomass burning. The technique is based on derivatization of the parent NACs by using N,O-bis-(trimethylsilyl)-trifluoro acetamide, one of the most prevalent derivatization reagent for analyzing hydroxylated molecules, followed by gas chromatography-mass spectrometry using electron ionization (EI) and methane chemical ionization (CI). This method is evaluated for 32 NACs including nitrophenols, methyl-/methoxy-nitrophenols, nitrobenzoic acids, and nitrobenzyl alcohols. Electron ionization spectra were characterized by a high abundance of ions corresponding to [M+ ] or [M+ - 15]. Chemical ionization spectra exhibited high abundance for [M+ + 1], [M+ - 15], and [M+ + 29] ions. Both EI and CI spectra exhibit ions specific to nitro group(s) for [M+ - 31], [M+ - 45], and [M+ - 60]. The strong abundance observed for [M+ ] (EI), [M+ - 15] (EI/CI), or [M+ + 1] (CI) ions is consistent with the high charge stabilizing ability associated with aromatic compounds. The combination of EI and CI ionization offers strong capabilities for detection and identification of NACs. Spectra associated with NACs, containing hydrogen, carbon, oxygen, and nitrogen atoms only, as silylated derivatives show fragment/adduct ions at either (a) odd or (b) even masses that indicate either (a) odd or (b) even number of nitro groups, respectively. Mass spectra associated with silylated NACs exhibited 3 distinct regions where characteristic fragmentation with a specific pattern associated with (1) ─OH and/or ─COOH groups, (2) ─NO2 group(s), and (3) benzene ring(s). These findings were confirmed with applications to chamber aerosol and ambient PM2.5 .

Dataset Information

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

Publications

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped, Centrosymmetric Diketopyrrolopyrroles.

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