The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents
<p dir="ltr">In this study, a D–A cycloalkanone (K1) has been investigated by steady state absorption and fluorescence in neat solvents and in three binary mixtures of nonpolar aprotic/polar protic, polar aprotic/polar protic, and polar protic/polar protic solvents. The experimental...
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2019
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| _version_ | 1864513552167993344 |
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| author | Ibrahim Ahmed Z. Al-Ansari (4846957) |
| author_facet | Ibrahim Ahmed Z. Al-Ansari (4846957) |
| author_role | author |
| dc.creator.none.fl_str_mv | Ibrahim Ahmed Z. Al-Ansari (4846957) |
| dc.date.none.fl_str_mv | 2019-04-16T21:00:00Z |
| dc.identifier.none.fl_str_mv | 10.1007/s00894-019-4015-6 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/journal_contribution/The_electronic_origin_of_the_ground_state_spectral_features_and_excited_state_deactivation_in_cycloalkanones_the_role_of_intermolecular_H-bonding_in_neat_and_binary_mixtures_of_solvents/21597126 |
| dc.rights.none.fl_str_mv | CC BY 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Chemical sciences Inorganic chemistry Information and computing sciences Theory of computation DFT TD-DFT NBO Cycloalkanones Binary-mixture Hyperconojugation |
| dc.title.none.fl_str_mv | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| dc.type.none.fl_str_mv | Text Journal contribution info:eu-repo/semantics/publishedVersion text contribution to journal |
| description | <p dir="ltr">In this study, a D–A cycloalkanone (K1) has been investigated by steady state absorption and fluorescence in neat solvents and in three binary mixtures of nonpolar aprotic/polar protic, polar aprotic/polar protic, and polar protic/polar protic solvents. The experimental findings were complemented by density functional theory (DFT), time-dependent density functional theory (TD-DFT), and NBO quantum-mechanical calculations. Experimentally, effective changes in absorption and fluorescence were observed by solute–solvent interaction. The binary K1-solvent1-solv2 configuration, modeled at the B3LYP-DFT level, confirms involvement of inter-molecular H-bonding with the carbonyl C=O in the fluorescence deactivation process (quenching). This is supported by considerable electron delocalization from C=O to the solvent’s hydroxyl (<i>n</i>O → σ*H-O). This type of hyperconjugation was found to be the main driver for solute–solvent stabilization.</p><h2>Other Information</h2><p dir="ltr">Published in: Journal of Molecular Modeling<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="http://dx.doi.org/10.1007/s00894-019-4015-6" target="_blank">http://dx.doi.org/10.1007/s00894-019-4015-6</a></p> |
| eu_rights_str_mv | openAccess |
| id | Manara2_2ed41981a13697f3b417a60576d4066e |
| identifier_str_mv | 10.1007/s00894-019-4015-6 |
| network_acronym_str | Manara2 |
| network_name_str | Manara2 |
| oai_identifier_str | oai:figshare.com:article/21597126 |
| publishDate | 2019 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY 4.0 |
| spelling | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solventsIbrahim Ahmed Z. Al-Ansari (4846957)Chemical sciencesInorganic chemistryInformation and computing sciencesTheory of computationDFTTD-DFTNBOCycloalkanonesBinary-mixtureHyperconojugation<p dir="ltr">In this study, a D–A cycloalkanone (K1) has been investigated by steady state absorption and fluorescence in neat solvents and in three binary mixtures of nonpolar aprotic/polar protic, polar aprotic/polar protic, and polar protic/polar protic solvents. The experimental findings were complemented by density functional theory (DFT), time-dependent density functional theory (TD-DFT), and NBO quantum-mechanical calculations. Experimentally, effective changes in absorption and fluorescence were observed by solute–solvent interaction. The binary K1-solvent1-solv2 configuration, modeled at the B3LYP-DFT level, confirms involvement of inter-molecular H-bonding with the carbonyl C=O in the fluorescence deactivation process (quenching). This is supported by considerable electron delocalization from C=O to the solvent’s hydroxyl (<i>n</i>O → σ*H-O). This type of hyperconjugation was found to be the main driver for solute–solvent stabilization.</p><h2>Other Information</h2><p dir="ltr">Published in: Journal of Molecular Modeling<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="http://dx.doi.org/10.1007/s00894-019-4015-6" target="_blank">http://dx.doi.org/10.1007/s00894-019-4015-6</a></p>2019-04-16T21:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1007/s00894-019-4015-6https://figshare.com/articles/journal_contribution/The_electronic_origin_of_the_ground_state_spectral_features_and_excited_state_deactivation_in_cycloalkanones_the_role_of_intermolecular_H-bonding_in_neat_and_binary_mixtures_of_solvents/21597126CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/215971262019-04-16T21:00:00Z |
| spellingShingle | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents Ibrahim Ahmed Z. Al-Ansari (4846957) Chemical sciences Inorganic chemistry Information and computing sciences Theory of computation DFT TD-DFT NBO Cycloalkanones Binary-mixture Hyperconojugation |
| status_str | publishedVersion |
| title | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| title_full | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| title_fullStr | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| title_full_unstemmed | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| title_short | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| title_sort | The electronic origin of the ground state spectral features and excited state deactivation in cycloalkanones: the role of intermolecular H-bonding in neat and binary mixtures of solvents |
| topic | Chemical sciences Inorganic chemistry Information and computing sciences Theory of computation DFT TD-DFT NBO Cycloalkanones Binary-mixture Hyperconojugation |