Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye
Thiophene ring-enhancing electron delocalization imparts unique properties to azoic chromophore tools. The novel TA-OH dye contains a push–pull π-electron system, including a thiophene-azo scaffold with a hydroxyl group at the <i>ortho</i> position to the azo bridge. The hydroxyl group i...
| Main Authors: | , , , , , , |
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| Format: | Article |
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MDPI AG
2023-12-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/14/1/31 |
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| author | Rosita Diana Lucia Sessa Simona Concilio Stefano Piotto Luigi Di Costanzo Antonio Carella Barbara Panunzi |
| author_facet | Rosita Diana Lucia Sessa Simona Concilio Stefano Piotto Luigi Di Costanzo Antonio Carella Barbara Panunzi |
| author_sort | Rosita Diana |
| collection | DOAJ |
| description | Thiophene ring-enhancing electron delocalization imparts unique properties to azoic chromophore tools. The novel TA-OH dye contains a push–pull π-electron system, including a thiophene-azo scaffold with a hydroxyl group at the <i>ortho</i> position to the azo bridge. The hydroxyl group is expected to lock the azo bridge in its <i>trans</i> conformation, concurring with the photostability and fastness of the dye. The single crystal analysis identified the molecule’s primary conjugation plane, and the theoretical analysis provided electronic pattern insights. The absorption behavior and the <i>trans</i>-to-<i>cis</i> conversion were examined from both experimental and theoretical perspectives. The effect of solvent polarity and the role of pH on the photophysical properties were explored. The solvent polarity strongly affects the absorbance spectrum of TA-OH, therefore potentially making NLO active. Additionally, TA-OH exhibited pH responsiveness akin to classic dichromatic pH indicators, with a noticeable color shift from red to blue observed as pH transitioned from neutral to alkaline. Absorbance titration experiments, along with experimental/theoretical determination of pKa, defined the pH sensing ability. |
| first_indexed | 2024-03-08T09:55:58Z |
| format | Article |
| id | doaj.art-9053a117a9284d29b19099acbf2c5d93 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-08T09:55:58Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-9053a117a9284d29b19099acbf2c5d932024-01-29T13:51:05ZengMDPI AGCrystals2073-43522023-12-011413110.3390/cryst14010031Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo DyeRosita Diana0Lucia Sessa1Simona Concilio2Stefano Piotto3Luigi Di Costanzo4Antonio Carella5Barbara Panunzi6Department of Agricultural Sciences, University of Naples Federico II, Via Università 100, 80055 Portici, ItalyDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, ItalyDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, ItalyDepartment of Pharmacy, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, ItalyDepartment of Agricultural Sciences, University of Naples Federico II, Via Università 100, 80055 Portici, ItalyDepartment of Chemical Sciences, University of Naples Federico II, Strada Comunale Cinthia, 26, 80126 Napoli, ItalyDepartment of Agricultural Sciences, University of Naples Federico II, Via Università 100, 80055 Portici, ItalyThiophene ring-enhancing electron delocalization imparts unique properties to azoic chromophore tools. The novel TA-OH dye contains a push–pull π-electron system, including a thiophene-azo scaffold with a hydroxyl group at the <i>ortho</i> position to the azo bridge. The hydroxyl group is expected to lock the azo bridge in its <i>trans</i> conformation, concurring with the photostability and fastness of the dye. The single crystal analysis identified the molecule’s primary conjugation plane, and the theoretical analysis provided electronic pattern insights. The absorption behavior and the <i>trans</i>-to-<i>cis</i> conversion were examined from both experimental and theoretical perspectives. The effect of solvent polarity and the role of pH on the photophysical properties were explored. The solvent polarity strongly affects the absorbance spectrum of TA-OH, therefore potentially making NLO active. Additionally, TA-OH exhibited pH responsiveness akin to classic dichromatic pH indicators, with a noticeable color shift from red to blue observed as pH transitioned from neutral to alkaline. Absorbance titration experiments, along with experimental/theoretical determination of pKa, defined the pH sensing ability.https://www.mdpi.com/2073-4352/14/1/31azo dyesthiophenetheoretical insightpH-responsivelightfastness |
| spellingShingle | Rosita Diana Lucia Sessa Simona Concilio Stefano Piotto Luigi Di Costanzo Antonio Carella Barbara Panunzi Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye Crystals azo dyes thiophene theoretical insight pH-responsive lightfastness |
| title | Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye |
| title_full | Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye |
| title_fullStr | Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye |
| title_full_unstemmed | Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye |
| title_short | Experimental and Theoretical Insights into a Novel Lightfast Thiophene Azo Dye |
| title_sort | experimental and theoretical insights into a novel lightfast thiophene azo dye |
| topic | azo dyes thiophene theoretical insight pH-responsive lightfastness |
| url | https://www.mdpi.com/2073-4352/14/1/31 |
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