Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer
In this study, we synthesized novel donor–π–acceptor (D–π–A) functional dyes bearing a carbonyl-bridged bithiophene as a π-conjugated spacer and evaluated the absorption and fluorescence properties as well as the photostability. The developed dyes <b>1-CO</b>–<b>3-CO</b> poss...
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2025-07-01
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| author | Miyu Ueda Ryo Nagayama Masaki Nagaoka Naoya Suzuki Shintaro Kodama Takeshi Maeda Shin-ichiro Kato Shigeyuki Yagi |
| author_facet | Miyu Ueda Ryo Nagayama Masaki Nagaoka Naoya Suzuki Shintaro Kodama Takeshi Maeda Shin-ichiro Kato Shigeyuki Yagi |
| author_sort | Miyu Ueda |
| collection | DOAJ |
| description | In this study, we synthesized novel donor–π–acceptor (D–π–A) functional dyes bearing a carbonyl-bridged bithiophene as a π-conjugated spacer and evaluated the absorption and fluorescence properties as well as the photostability. The developed dyes <b>1-CO</b>–<b>3-CO</b> possess an <i>N</i>,<i>N</i>-diphenylaminophenyl electron donor unit and an electron acceptor unit such as a formyl group (<b>1-CO</b>), an (<i>N</i>,<i>N</i>-diethylthiobarbituryl)methylene moiety (<b>2-CO</b>), or a (3-dicyanomethylidene-1-indanon-2-yl)methylene moiety (<b>3-CO</b>). The absorption spectra of <b>1-CO</b>–<b>3-CO</b> in dichloromethane at room temperature showed absorption maxima at 569 nm, 631 nm, and 667 nm, respectively, and the stronger acceptors in <b>2-CO</b> and <b>3-CO</b> led to enhancement of the ICT character. In addition, <b>2-CO</b> and <b>3-CO</b> had a second absorption band in the visible region, showing panchromatic absorption properties. Electrochemical analyses of the developed dyes revealed that the carbonyl bridging group in the π-spacer contributes to stabilization of the frontier orbitals such as the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively), in comparison with the referential dyes bearing a dibutylmethylene-bridged bithiophene spacer, <b>1-CBu<sub>2</sub></b>–<b>3-CBu<sub>2</sub></b>. The HOMO/LUMO stabilization brought about high photostability in the doped poly(methyl methacrylate) film. |
| format | Article |
| id | doaj-art-2ed14e619014472697bdb07f51bda90c |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-07-01 |
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| series | Molecules |
| spelling | doaj-art-2ed14e619014472697bdb07f51bda90c2025-08-20T04:00:50ZengMDPI AGMolecules1420-30492025-07-013015308410.3390/molecules30153084Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-SpacerMiyu Ueda0Ryo Nagayama1Masaki Nagaoka2Naoya Suzuki3Shintaro Kodama4Takeshi Maeda5Shin-ichiro Kato6Shigeyuki Yagi7Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai 599-8531, Osaka, JapanIn this study, we synthesized novel donor–π–acceptor (D–π–A) functional dyes bearing a carbonyl-bridged bithiophene as a π-conjugated spacer and evaluated the absorption and fluorescence properties as well as the photostability. The developed dyes <b>1-CO</b>–<b>3-CO</b> possess an <i>N</i>,<i>N</i>-diphenylaminophenyl electron donor unit and an electron acceptor unit such as a formyl group (<b>1-CO</b>), an (<i>N</i>,<i>N</i>-diethylthiobarbituryl)methylene moiety (<b>2-CO</b>), or a (3-dicyanomethylidene-1-indanon-2-yl)methylene moiety (<b>3-CO</b>). The absorption spectra of <b>1-CO</b>–<b>3-CO</b> in dichloromethane at room temperature showed absorption maxima at 569 nm, 631 nm, and 667 nm, respectively, and the stronger acceptors in <b>2-CO</b> and <b>3-CO</b> led to enhancement of the ICT character. In addition, <b>2-CO</b> and <b>3-CO</b> had a second absorption band in the visible region, showing panchromatic absorption properties. Electrochemical analyses of the developed dyes revealed that the carbonyl bridging group in the π-spacer contributes to stabilization of the frontier orbitals such as the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively), in comparison with the referential dyes bearing a dibutylmethylene-bridged bithiophene spacer, <b>1-CBu<sub>2</sub></b>–<b>3-CBu<sub>2</sub></b>. The HOMO/LUMO stabilization brought about high photostability in the doped poly(methyl methacrylate) film.https://www.mdpi.com/1420-3049/30/15/3084donor–π–acceptor-type dyeintramolecular charge transferpanchromatic absorptionphotostabilityfrontier orbital |
| spellingShingle | Miyu Ueda Ryo Nagayama Masaki Nagaoka Naoya Suzuki Shintaro Kodama Takeshi Maeda Shin-ichiro Kato Shigeyuki Yagi Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer Molecules donor–π–acceptor-type dye intramolecular charge transfer panchromatic absorption photostability frontier orbital |
| title | Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer |
| title_full | Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer |
| title_fullStr | Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer |
| title_full_unstemmed | Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer |
| title_short | Synthesis and Electronic Properties of Novel Donor–π–Acceptor-Type Functional Dyes with a Carbonyl-Bridged Bithiophene π-Spacer |
| title_sort | synthesis and electronic properties of novel donor π acceptor type functional dyes with a carbonyl bridged bithiophene π spacer |
| topic | donor–π–acceptor-type dye intramolecular charge transfer panchromatic absorption photostability frontier orbital |
| url | https://www.mdpi.com/1420-3049/30/15/3084 |
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