Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group
A very active branch of organic chemistry is putting great effort in tailoring fluorescent dyes for a myriad of applications, from technological to bioanalytical and biomedical applications. Among the major families of fluorophores, those derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODI...
| Main Authors: | , , , , , , , , , , , , , , |
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| Format: | Article |
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Royal Society of Chemistry
2016
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| Online Access: | https://eprints.nottingham.ac.uk/37842/ |
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| author | Orte, Angel Debroye, Elke Ruedas-Rama, Maria J. Garcia-Fernandez, Emilio Robinson, David Crovetto, Luis Talavera, Eva M. Alvarez-Pez, Jose M. Leen, Volker Verbelen, Bram Dias de Rezende, Lucas Cunha Dehaen, Wim Hofkens, Johan Van der Auweraer, Mark Boens, Noël |
| author_facet | Orte, Angel Debroye, Elke Ruedas-Rama, Maria J. Garcia-Fernandez, Emilio Robinson, David Crovetto, Luis Talavera, Eva M. Alvarez-Pez, Jose M. Leen, Volker Verbelen, Bram Dias de Rezende, Lucas Cunha Dehaen, Wim Hofkens, Johan Van der Auweraer, Mark Boens, Noël |
| author_sort | Orte, Angel |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | A very active branch of organic chemistry is putting great effort in tailoring fluorescent dyes for a myriad of applications, from technological to bioanalytical and biomedical applications. Among the major families of fluorophores, those derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY dyes) are undergoing a recent boost thanks to the simplicity and robustness of the chemistry involved. The BODIPY core can be modified with numerous side groups, the 8-position being a modification place with important effects on the spectroscopic and photophysical properties of the resulting dyes. Likewise, previous work has shown that the addition of groups attached at the 3- and 2-positions can result in dyes with very different properties. Herein, we generalize the effect of the substituent side groups by studying nine BODIPY dyes substituted with a phenyl, styryl or phenylethynyl moiety at the 2-, 3- or 8-position of the BODIPY scaffold. Within the class of phenyl- or phenylethynyl-substituted dyes, substitution at the 2-position always leads to dyes with the broadest bandwidths and the largest Stokes shifts. We investigate the solvent effect on the spectroscopic properties of the dyes, using four empirical solvent scales (dipolarity, polarizability, acidity and basicity: Catalán, J. Phys. Chem., 2009, 113, 5951). These analyses identify solvent dipolarity and polarizability as critical parameters accounting for the observed solvent-dependent shifts of the absorption and emission maxima. Finally, time-dependent density functional theory calculations provide insights into the structural and energetic issues concerning the spectroscopic properties of these fluorophores. |
| first_indexed | 2025-11-14T19:33:47Z |
| format | Article |
| id | nottingham-37842 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:33:47Z |
| publishDate | 2016 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-378422020-05-04T18:16:10Z https://eprints.nottingham.ac.uk/37842/ Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group Orte, Angel Debroye, Elke Ruedas-Rama, Maria J. Garcia-Fernandez, Emilio Robinson, David Crovetto, Luis Talavera, Eva M. Alvarez-Pez, Jose M. Leen, Volker Verbelen, Bram Dias de Rezende, Lucas Cunha Dehaen, Wim Hofkens, Johan Van der Auweraer, Mark Boens, Noël A very active branch of organic chemistry is putting great effort in tailoring fluorescent dyes for a myriad of applications, from technological to bioanalytical and biomedical applications. Among the major families of fluorophores, those derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY dyes) are undergoing a recent boost thanks to the simplicity and robustness of the chemistry involved. The BODIPY core can be modified with numerous side groups, the 8-position being a modification place with important effects on the spectroscopic and photophysical properties of the resulting dyes. Likewise, previous work has shown that the addition of groups attached at the 3- and 2-positions can result in dyes with very different properties. Herein, we generalize the effect of the substituent side groups by studying nine BODIPY dyes substituted with a phenyl, styryl or phenylethynyl moiety at the 2-, 3- or 8-position of the BODIPY scaffold. Within the class of phenyl- or phenylethynyl-substituted dyes, substitution at the 2-position always leads to dyes with the broadest bandwidths and the largest Stokes shifts. We investigate the solvent effect on the spectroscopic properties of the dyes, using four empirical solvent scales (dipolarity, polarizability, acidity and basicity: Catalán, J. Phys. Chem., 2009, 113, 5951). These analyses identify solvent dipolarity and polarizability as critical parameters accounting for the observed solvent-dependent shifts of the absorption and emission maxima. Finally, time-dependent density functional theory calculations provide insights into the structural and energetic issues concerning the spectroscopic properties of these fluorophores. Royal Society of Chemistry 2016-10-21 Article PeerReviewed Orte, Angel, Debroye, Elke, Ruedas-Rama, Maria J., Garcia-Fernandez, Emilio, Robinson, David, Crovetto, Luis, Talavera, Eva M., Alvarez-Pez, Jose M., Leen, Volker, Verbelen, Bram, Dias de Rezende, Lucas Cunha, Dehaen, Wim, Hofkens, Johan, Van der Auweraer, Mark and Boens, Noël (2016) Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group. RSC Advances, 6 . pp. 102899-102913. ISSN 2046-2069 Fluorescent dyes solvent effect Catalán solvent scales quantum chemical calculations http://pubs.rsc.org/en/Content/ArticleLanding/2016/RA/C6RA22340K#!divAbstract doi:10.1039/C6RA22340K doi:10.1039/C6RA22340K |
| spellingShingle | Fluorescent dyes solvent effect Catalán solvent scales quantum chemical calculations Orte, Angel Debroye, Elke Ruedas-Rama, Maria J. Garcia-Fernandez, Emilio Robinson, David Crovetto, Luis Talavera, Eva M. Alvarez-Pez, Jose M. Leen, Volker Verbelen, Bram Dias de Rezende, Lucas Cunha Dehaen, Wim Hofkens, Johan Van der Auweraer, Mark Boens, Noël Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title | Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title_full | Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title_fullStr | Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title_full_unstemmed | Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title_short | Effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of BODIPY dyes with a phenyl, styryl or phenylethynyl group |
| title_sort | effect of the substitution position (2, 3 or 8) on the spectroscopic and photophysical properties of bodipy dyes with a phenyl, styryl or phenylethynyl group |
| topic | Fluorescent dyes solvent effect Catalán solvent scales quantum chemical calculations |
| url | https://eprints.nottingham.ac.uk/37842/ https://eprints.nottingham.ac.uk/37842/ https://eprints.nottingham.ac.uk/37842/ |