Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study
On the basis of thieno(3,2-<i>b</i>)thiophene and dithieno[3,2-<i>b</i>:2′,3′-<i>d</i>]thiophene (<b>T2</b> and <b>T3</b> moieties) as π-linker, the <b>A</b>, <b>D</b> and <b>S</...
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MDPI AG
2019-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/17/3134 |
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| author | Zhi-Dan Sun Jiang-Shan Zhao Xue-Hai Ju Qi-Ying Xia |
| author_facet | Zhi-Dan Sun Jiang-Shan Zhao Xue-Hai Ju Qi-Ying Xia |
| author_sort | Zhi-Dan Sun |
| collection | DOAJ |
| description | On the basis of thieno(3,2-<i>b</i>)thiophene and dithieno[3,2-<i>b</i>:2′,3′-<i>d</i>]thiophene (<b>T2</b> and <b>T3</b> moieties) as π-linker, the <b>A</b>, <b>D</b> and <b>S</b> series dyes were designed to investigate the effect of the introducing N<sup>+</sup> as an “electron trap” into <b>T2</b> and <b>T3</b> on the properties of the dyes. The optimized structures, electronic and optical properties were investigated by the density functional theory (DFT) and time-dependent DFT (TD-DFT). The results show that the properties of the dyes are sensitive to the N<sup>+</sup> position in π-linkers. <b>D</b> series dyes with electron-withdrawing units located near the donor have better properties than the corresponding <b>A</b> series with the electron-withdrawing units located near the acceptor. For <b>A</b> and <b>D</b> series, the N<sup>+</sup> modified dye named <b>T2N+1-d</b> displays the largest red shift of the UV−vis absorption, the maximum integral values of the adsorption-wavelength curves over the visible light, the highest light harvesting efficiency (LHE, 0.996), and the strongest adsorption energy (−44.33 kcal/mol). <b>T2N+1-d</b> also has a large driving force of hole injection (Δ<i>G</i><sub>inj</sub>, −0.74 eV), which results in a more efficient hole injection. Bearing a lengthier π-linker than <b>T2N+1-d</b>, the properties of <b>T2N+1-s</b> are further improved. <b>T2N+1-d</b> moiety or its increased conjugated derivatives may be a promising π-linker. |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-22T00:18:55Z |
| publishDate | 2019-08-01 |
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| spelling | doaj.art-7b1e21ea6aa84ac0a8626a43ceb8f7cc2022-12-21T18:45:14ZengMDPI AGMolecules1420-30492019-08-012417313410.3390/molecules24173134molecules24173134Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT StudyZhi-Dan Sun0Jiang-Shan Zhao1Xue-Hai Ju2Qi-Ying Xia3Key Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, ChinaKey Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, ChinaKey Laboratory of Soft Chemistry and Functional Materials of MOE, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, ChinaSchool of Chemistry and Chemical Engineering, Linyi University, Linyi 276005, ChinaOn the basis of thieno(3,2-<i>b</i>)thiophene and dithieno[3,2-<i>b</i>:2′,3′-<i>d</i>]thiophene (<b>T2</b> and <b>T3</b> moieties) as π-linker, the <b>A</b>, <b>D</b> and <b>S</b> series dyes were designed to investigate the effect of the introducing N<sup>+</sup> as an “electron trap” into <b>T2</b> and <b>T3</b> on the properties of the dyes. The optimized structures, electronic and optical properties were investigated by the density functional theory (DFT) and time-dependent DFT (TD-DFT). The results show that the properties of the dyes are sensitive to the N<sup>+</sup> position in π-linkers. <b>D</b> series dyes with electron-withdrawing units located near the donor have better properties than the corresponding <b>A</b> series with the electron-withdrawing units located near the acceptor. For <b>A</b> and <b>D</b> series, the N<sup>+</sup> modified dye named <b>T2N+1-d</b> displays the largest red shift of the UV−vis absorption, the maximum integral values of the adsorption-wavelength curves over the visible light, the highest light harvesting efficiency (LHE, 0.996), and the strongest adsorption energy (−44.33 kcal/mol). <b>T2N+1-d</b> also has a large driving force of hole injection (Δ<i>G</i><sub>inj</sub>, −0.74 eV), which results in a more efficient hole injection. Bearing a lengthier π-linker than <b>T2N+1-d</b>, the properties of <b>T2N+1-s</b> are further improved. <b>T2N+1-d</b> moiety or its increased conjugated derivatives may be a promising π-linker.https://www.mdpi.com/1420-3049/24/17/3134<i>p</i>-type dye-sensitized solar cells (DSSCs)dyesπ-linkeramine saltdensity functional theory (DFT) |
| spellingShingle | Zhi-Dan Sun Jiang-Shan Zhao Xue-Hai Ju Qi-Ying Xia Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study Molecules <i>p</i>-type dye-sensitized solar cells (DSSCs) dyes π-linker amine salt density functional theory (DFT) |
| title | Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study |
| title_full | Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study |
| title_fullStr | Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study |
| title_full_unstemmed | Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study |
| title_short | Effect of Nitrogen Cation as “Electron Trap” at π-Linker on Properties for <i>p</i>-Type Photosensitizers: DFT Study |
| title_sort | effect of nitrogen cation as electron trap at π linker on properties for i p i type photosensitizers dft study |
| topic | <i>p</i>-type dye-sensitized solar cells (DSSCs) dyes π-linker amine salt density functional theory (DFT) |
| url | https://www.mdpi.com/1420-3049/24/17/3134 |
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