Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution
The identification of novel molecular systems with high fluorescence and significant non-linear optical (NLO) properties is a hot topic in the continuous search for new emissive probes. Here, the photobehavior of three two-arm bis[(dimethylamino)styryl]benzene derivatives, where the central benzene...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/24/8725 |
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| author | Letizia Mencaroni Alessio Cesaretti Benedetta Carlotti Martina Alebardi Fausto Elisei Ana Ratković Irena Škorić Anna Spalletti |
| author_facet | Letizia Mencaroni Alessio Cesaretti Benedetta Carlotti Martina Alebardi Fausto Elisei Ana Ratković Irena Škorić Anna Spalletti |
| author_sort | Letizia Mencaroni |
| collection | DOAJ |
| description | The identification of novel molecular systems with high fluorescence and significant non-linear optical (NLO) properties is a hot topic in the continuous search for new emissive probes. Here, the photobehavior of three two-arm bis[(dimethylamino)styryl]benzene derivatives, where the central benzene was replaced by pyridine, furan, or thiophene, was studied by stationary and time-resolved spectroscopic techniques with ns and fs resolution. The three molecules under investigation all showed positive fluorosolvatochromism, due to intramolecular charge-transfer (ICT) dynamics from the electron-donor dimethylamino groups, and significant fluorescence quantum yields, because of the population of a planar and emissive ICT state stabilized by intramolecular hydrogen-bond-like interactions. The NLO properties (hyperpolarizability coefficient and TPA cross-section) were also measured. The obtained results allowed the role of the central heteroaromatic ring to be disclosed. In particular, the introduction of the thiophene ring guarantees high fluorescent quantum yields irrespective of the polarity of the medium, and the largest hyperpolarizability coefficient because of the increased conjugation. An important and structure-dependent involvement of the triplet state was also highlighted, with the intersystem crossing being competitive with fluorescence, especially in the thiophene derivative, where the triplet was found to significantly sensitize molecular oxygen even in polar environment, leading to possible applications in photodynamic therapy. |
| first_indexed | 2024-03-09T16:03:45Z |
| format | Article |
| id | doaj.art-f61615ff4ffc44f19c493432c360188f |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T16:03:45Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f61615ff4ffc44f19c493432c360188f2023-11-24T16:56:21ZengMDPI AGMolecules1420-30492022-12-012724872510.3390/molecules27248725Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic SubstitutionLetizia Mencaroni0Alessio Cesaretti1Benedetta Carlotti2Martina Alebardi3Fausto Elisei4Ana Ratković5Irena Škorić6Anna Spalletti7Department of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyDepartment of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyDepartment of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyDepartment of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyDepartment of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyDepartment of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, HR-10 000 Zagreb, CroatiaDepartment of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, HR-10 000 Zagreb, CroatiaDepartment of Chemistry, Biology and Biotechnology and Center of Excellence on Innovative Nanostructured Materials (CEMIN), University of Perugia, Via Elce di Sotto n.8, 06123 Perugia, ItalyThe identification of novel molecular systems with high fluorescence and significant non-linear optical (NLO) properties is a hot topic in the continuous search for new emissive probes. Here, the photobehavior of three two-arm bis[(dimethylamino)styryl]benzene derivatives, where the central benzene was replaced by pyridine, furan, or thiophene, was studied by stationary and time-resolved spectroscopic techniques with ns and fs resolution. The three molecules under investigation all showed positive fluorosolvatochromism, due to intramolecular charge-transfer (ICT) dynamics from the electron-donor dimethylamino groups, and significant fluorescence quantum yields, because of the population of a planar and emissive ICT state stabilized by intramolecular hydrogen-bond-like interactions. The NLO properties (hyperpolarizability coefficient and TPA cross-section) were also measured. The obtained results allowed the role of the central heteroaromatic ring to be disclosed. In particular, the introduction of the thiophene ring guarantees high fluorescent quantum yields irrespective of the polarity of the medium, and the largest hyperpolarizability coefficient because of the increased conjugation. An important and structure-dependent involvement of the triplet state was also highlighted, with the intersystem crossing being competitive with fluorescence, especially in the thiophene derivative, where the triplet was found to significantly sensitize molecular oxygen even in polar environment, leading to possible applications in photodynamic therapy.https://www.mdpi.com/1420-3049/27/24/8725fluorescencesolvatochromismDFT quantum mechanical calculationsnonlinear optical propertiesultrafast spectroscopyintersystem crossing |
| spellingShingle | Letizia Mencaroni Alessio Cesaretti Benedetta Carlotti Martina Alebardi Fausto Elisei Ana Ratković Irena Škorić Anna Spalletti Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution Molecules fluorescence solvatochromism DFT quantum mechanical calculations nonlinear optical properties ultrafast spectroscopy intersystem crossing |
| title | Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution |
| title_full | Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution |
| title_fullStr | Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution |
| title_full_unstemmed | Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution |
| title_short | Tuning the Photophysics of Two-Arm Bis[(dimethylamino)styryl]benzene Derivatives by Heterocyclic Substitution |
| title_sort | tuning the photophysics of two arm bis dimethylamino styryl benzene derivatives by heterocyclic substitution |
| topic | fluorescence solvatochromism DFT quantum mechanical calculations nonlinear optical properties ultrafast spectroscopy intersystem crossing |
| url | https://www.mdpi.com/1420-3049/27/24/8725 |
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