Disubstituted pyrenes at the non-K region by the same or different (hetero)aryl groups have proven to be an increasingly interesting area of research for scientists over the last decade due to their optical and photophysical properties. However, in this area, there is no systematization of the structures and synthesis methods nor their limitations. In this review, all approaches to the synthesis of these compounds, starting from the commercially available pyrene are described. Herein, the ways of obtaining of disubstituted intermediates based on bromination and acylation reaction are presented. This is crucial in the determination of the possibility of further functionalization by using coupling, cycloaddition, condensation, etc. reactions. Moreover, the application of disubstituted pyrenes in the synthesis of 1,3,6,8-tetrasubstituted was also reviewed. This review describes the directions of research on chemistry of disubstituted pyrenes.
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http://dx.doi.org/10.3390/molecules24142551 | DOI Listing |
Molecules
December 2022
Laboratoire de Chimie Théorique de Bio- et Nanosystemes, Faculty of Exact Sciences, University Djillali Liabes of Sidi Bel-Abbes, B.P. 89, Sidi Bel Abbes 22000, Algeria.
Results of a theoretical study devoted to comparing NLO (non-linear optics) responses of derivatives of tetracene, isochrysene, and pyrene are reported. The static hyperpolarizability β, the dipole moment μ, the HOMO and LUMO orbitals, and their energy gap were calculated using the CAM-B3LYP density functional combined with the cc-pVDZ basis set. The para-disubstituted NO-tetracene-N(CH) has the highest NLO response, which is related to a large intramolecular charge transfer.
View Article and Find Full Text PDFMol Divers
April 2023
Department of Chemical Engineering and Applied Chemistry, College of Chemistry, Jilin University, Changchun, 130012, People's Republic of China.
Herein, we developed a convenient and efficient method via protonation of p-toluenesulfonic acid promoted cyclocondensation of o-phenylenediamine and aldehydes for selectively synthesizing 1,2-disubstituted benzimidazoles. This method displayed broad substrate adaptability and afforded the desired products in moderate to excellent yield in short reaction time. The effect of different substituents on the yield was investigated by extending optimum reaction conditions, which was further confirmed by theoretical calculations.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2022
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610064, China.
Several γ-cyclodextrin (CD) derivatives mono- or di-substituted by pyrenes at the primary rim of the CD were demonstrated to aggregate into nano-strips in aqueous solutions, with the pyrene moieties interpenetrating into γ-CD cavities. The hydrophobic complexation-induced aggregation provides a rigid chiral environment for the pyrenes and leads to significant electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) activities, giving unprecedently high g and g values up to 4.3×10 and 5.
View Article and Find Full Text PDFChemistry
February 2021
Institut für Anorganische Chemie and, Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm .
View Article and Find Full Text PDFBeilstein J Nanotechnol
September 2020
Physics Department E20, Technical University of Munich, James-Franck-Straße 1, D-85748 Garching, Germany.
The controlled modification of electronic and photophysical properties of polycyclic aromatic hydrocarbons by chemical functionalization, adsorption on solid supports, and supramolecular organization is the key to optimize the application of these compounds in (opto)electronic devices. Here, we present a multimethod study comprehensively characterizing a family of pyridin-4-ylethynyl-functionalized pyrene derivatives in different environments. UV-vis measurements in toluene solutions revealed absorption at wavelengths consistent with density functional theory (DFT) calculations, while emission experiments showed a high fluorescence quantum yield.
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