Polarized, V-Shaped, and Conjoined Biscoumarins: From Lack of Dipole Moment Alignment to High Brightness

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dc.contributor.authorKielesiński, Łukasz
dc.contributor.authorDeperasińska, Irena
dc.contributor.authorMorawski, Olaf
dc.contributor.authorVygranenko, Kateryna V.
dc.contributor.authorOuellette, Erik T.
dc.contributor.authorGryko, Daniel T.
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciencesen
dc.contributor.organizationInstitute of Physics, Polish Academy of Sciencesen
dc.contributor.organizationDepartment of Chemistry, University of Californiaen
dc.contributor.organizationChemical Sciences Division, Lawrence Berkeley National Laboratoryen
dc.date.accessioned2022-09-06T13:35:39Z
dc.date.available2022-09-06T13:35:39Z
dc.date.issued2022
dc.description.abstractEleven conjoined coumarins possessing a chromeno[3,4-c]chromene-6,7-dione skeleton have been synthesized via the reaction of electron-rich phenols with esters of coumarin-3-carboxylic acids, catalyzed by either Lewis acids or 4-dimethylaminopyridine. Furthermore, Michael-type addition to angular benzo[f]coumarins is possible, leading to conjugated helical systems. Arrangement of the electron-donating amino groups at diverse positions on this heterocyclic skeleton makes it possible to obtain π-expanded coumarins with emission either sensitive to, or entirely independent of, solvent polarity with large Stokes shifts. Computational studies have provided a rationale for moderate solvatochromic effects unveiling the lack of collinearity of the dipole moments in the ground and excited states. Depending on the functional groups present, the obtained dyes are highly polarized with dipole moments of ∼14 D in the ground state and ∼20–25 D in the excited state. Strong emission in nonpolar solvents, in spite of the inclusion of a NO2 group, is rationalized by the fact that the intramolecular charge transfer introduced into these molecules is strong enough to suppress intersystem crossing yet weak enough to prevent the formation of dark twisted intramolecular charge transfer states. Photochemical transformation of the dye possessing a chromeno[3,4-c]pyridine-4,5-dione scaffold led to the formation of a spirocyclic benzo[g]coumarin.en
dc.description.sponsorshipPolish National Science Center, Poland (OPUS 2020/37/B/ST4/00017) QuantERA programme─project 2017/25/Z/ST2/03038 Foundation for Polish Science (TEAM POIR.04.04.00-00-3CF4/16-00) EU’s Horizon 2020 research and innovation programme under grant agreement no 860762 (MSC ITN CHAIR) Director, Office of Science, Office of Basic Energy Sciences, of the U.S. DOE under contract no. DE-AC02-05CH11231
dc.identifier.citationJ. Org. Chem. 2022, 87, 5961−5975 . https://doi.org/10.1021/acs.joc.2c00232en
dc.identifier.doi10.1021/acs.joc.2c00232
dc.identifier.issn0022-3263
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/21606
dc.language.isoen
dc.publisherAmerican Chemical Societyen
dc.rightsUznanie autorstwa 4.0 Międzynarodowe*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectaromatic compoundsen
dc.subjectdyes and pigmentsen
dc.subjecthydrocarbonsen
dc.subjectmolecular structureen
dc.subjectmoleculesen
dc.titlePolarized, V-Shaped, and Conjoined Biscoumarins: From Lack of Dipole Moment Alignment to High Brightnessen
dc.typearticleen
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