N-Aryl substituents have an influence on the photophysics of tetraaryl-pyrrolo[3,2-b]pyrroles

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dc.contributor.authorPetrykowski, Wojciech D.
dc.contributor.authorBanasiewicz, Marzena
dc.contributor.authorMorawski, Olaf
dc.contributor.authorKałuża, Zbigniew
dc.contributor.authorBarboza, Cristina A.
dc.contributor.authorGryko, Daniel T.
dc.contributor.organizationInstitute of Organic Chemistry, Polish Academy of Sciences
dc.contributor.organizationInstitute of Physics, Polish Academy of Sciences
dc.date.accessioned2026-02-02T05:10:52Z
dc.date.available2026-02-02T05:10:52Z
dc.date.issued2026
dc.date.submitted2026-01-30T12:05:52Zen
dc.description.abstractThe photophysics of two series of 1,4-dihydro-tetraaryl-pyrrolo[3,2-b]pyrroles possessing N-aryl substituents with various electronic characteristics was investigated systematically. The molecular structure of these compounds was designed so that their solubility enabled us to study their absorption and emission in a broad range of solvents. The presence of N-4-nitrophenyl substituents is responsible for a weak charge-transfer absorption band and shifts the emission band hypsochromically. At the same time, their presence quenches fluorescence; although if electron-withdrawing substituents are present at positions 2 and 5, this effect is reduced by an order of magnitude. In the case of less electron-withdrawing N-4-cyanophenyl and N-3-cyanophenyl groups, strong emission is present only if the electron-withdrawing groups are located at positions 2 and 5. The combined experimental and computational study points out the existence of a barrier between au (bright) and ag (dark) CT states, the height of which is the key factor governing the fate of these molecules in the excited state. Weaker electronic communication at positions 1 and 4 of the DHPP core is responsible for strong charge separation. Polar solvents favor the formation of transient dipole moments due to excited-state symmetry-breaking, which amplifies the nonradiative deactivation of nitro-TAPPs. A large increase in fluorescence intensity at 77 K suggests that internal conversion is a key channel for non-radiative electronic relaxation. Conversely, moderate to weak electron-donating groups favor strong LE emission.en
dc.description.sponsorshipEuropean Union’s Horizon 2020 Research and Innovation Programunder the Marie Skłodowska-Curie grant agreement no. 101007804; European Research Council (ARCHIMEDES, 101097337); Polish National Science Centre (OPUS 2020/37/B/ST4/00017); Polish high-performance computing infrastructure PLGrid (HPC Center: ACK Cyfronet AGH) grant no. PLG/2024/017465.
dc.identifier.citationPhys. Chem. Chem. Phys., 2026, 28, 2344-2352 // https://doi.org/10.1039/D5CP03474D
dc.identifier.doi10.1039/D5CP03474D
dc.identifier.issn1463-9076
dc.identifier.issn1463-9084
dc.identifier.urihttps://open.icm.edu.pl/handle/123456789/26469
dc.language.isoen
dc.publisherRoyal Society of Chemistry
dc.relation.ispartofseries28
dc.rightsUznanie autorstwa-Użycie niekomercyjne 3.0 Unporteden
dc.rights.urihttp://creativecommons.org/licenses/by-nc/3.0/
dc.sourcePhysical Chemistry Chemical Physics
dc.titleN-Aryl substituents have an influence on the photophysics of tetraaryl-pyrrolo[3,2-b]pyrrolesen
dc.typearticle
dc.type.versionpublishedVersion
person.identifier.orcidGryko, Daniel T. [0000-0002-2146-1282]
person.identifier.orcidPetrykowski Wojciech D. [0009-0007-5490-8371]
person.identifier.orcidBanasiewicz, Marzena [0000-0002-8251-5440]
person.identifier.orcidMorawski, Olaf [0000-0002-9475-668X]
person.identifier.orcidBarboza, Cristina A. [0000-0001-8257-3862]
person.identifier.orcidKałuża, Zbigniew [0000-0002-9548-0080]
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