Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity
Abstract The effects of halide ligands on the photoluminescence (PL) and photoredox properties were examined on [IrAu12(dppe)5X2]+ (1X; X=Cl, Br, I; dppe=1,2‐bis(diphenylphosphino)ethane). The PL quantum yield was enhanced in the order of 1Cl (67 %)<1Br (75 %)<1I (77 %). The lifetime of the ph...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2024-03-01
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| Series: | ChemElectroChem |
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| Online Access: | https://doi.org/10.1002/celc.202300669 |
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| author | Dr. Haru Hirai Prof. Dr. Shinjiro Takano Prof. Dr. Shinya Masuda Prof. Dr. Tatsuya Tsukuda |
| author_facet | Dr. Haru Hirai Prof. Dr. Shinjiro Takano Prof. Dr. Shinya Masuda Prof. Dr. Tatsuya Tsukuda |
| author_sort | Dr. Haru Hirai |
| collection | DOAJ |
| description | Abstract The effects of halide ligands on the photoluminescence (PL) and photoredox properties were examined on [IrAu12(dppe)5X2]+ (1X; X=Cl, Br, I; dppe=1,2‐bis(diphenylphosphino)ethane). The PL quantum yield was enhanced in the order of 1Cl (67 %)<1Br (75 %)<1I (77 %). The lifetime of the photoexcited state was shortened in the order of 1Cl>1Br>1I due to the acceleration of radiative relaxation by the heavy atom effect in 1I. Despite the shortest PL lifetime, cluster 1I exhibited the highest conversion in the photocatalytic [2+2] cycloaddition of bisenone. The PL from 1Cl and 1Br was quenched by adding Lewis acid Li+, required for activation of bisenone, whereas that from 1I remained unaffected. Theoretical calculations showed that the Au−Cl and Au−Br bonds of 1Cl and 1Br were weakened by interaction with Li+, while the Au−I bond of 1I was not. Clusters 1Cl and 1Br underwent halide exchange with isocyanide in the presence of Li+, whereas 1I did not. These results suggested that the photoredox activity of 1Cl and 1Br was suppressed by the Li+‐induced nonradiative quenching of the photoexcited state. This study highlights the unexpected importance of halide ligands in the design of efficient cluster photocatalysts. |
| first_indexed | 2024-03-07T18:39:22Z |
| format | Article |
| id | doaj.art-790e34aa80f0434985d0ad1cdc2e033c |
| institution | Directory Open Access Journal |
| issn | 2196-0216 |
| language | English |
| last_indexed | 2024-03-07T18:39:22Z |
| publishDate | 2024-03-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemElectroChem |
| spelling | doaj.art-790e34aa80f0434985d0ad1cdc2e033c2024-03-02T04:26:52ZengWiley-VCHChemElectroChem2196-02162024-03-01115n/an/a10.1002/celc.202300669Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox ActivityDr. Haru Hirai0Prof. Dr. Shinjiro Takano1Prof. Dr. Shinya Masuda2Prof. Dr. Tatsuya Tsukuda3Department of Chemistry Graduate School of Science The University of Tokyo 7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 JapanDepartment of Chemistry Graduate School of Science The University of Tokyo 7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 JapanDepartment of Chemistry Graduate School of Science The University of Tokyo 7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 JapanDepartment of Chemistry Graduate School of Science The University of Tokyo 7-3-1 Hongo Bunkyo-ku Tokyo 113-0033 JapanAbstract The effects of halide ligands on the photoluminescence (PL) and photoredox properties were examined on [IrAu12(dppe)5X2]+ (1X; X=Cl, Br, I; dppe=1,2‐bis(diphenylphosphino)ethane). The PL quantum yield was enhanced in the order of 1Cl (67 %)<1Br (75 %)<1I (77 %). The lifetime of the photoexcited state was shortened in the order of 1Cl>1Br>1I due to the acceleration of radiative relaxation by the heavy atom effect in 1I. Despite the shortest PL lifetime, cluster 1I exhibited the highest conversion in the photocatalytic [2+2] cycloaddition of bisenone. The PL from 1Cl and 1Br was quenched by adding Lewis acid Li+, required for activation of bisenone, whereas that from 1I remained unaffected. Theoretical calculations showed that the Au−Cl and Au−Br bonds of 1Cl and 1Br were weakened by interaction with Li+, while the Au−I bond of 1I was not. Clusters 1Cl and 1Br underwent halide exchange with isocyanide in the presence of Li+, whereas 1I did not. These results suggested that the photoredox activity of 1Cl and 1Br was suppressed by the Li+‐induced nonradiative quenching of the photoexcited state. This study highlights the unexpected importance of halide ligands in the design of efficient cluster photocatalysts.https://doi.org/10.1002/celc.202300669Cluster compoundsGoldHalidesLuminescencePhotoredox catalysis |
| spellingShingle | Dr. Haru Hirai Prof. Dr. Shinjiro Takano Prof. Dr. Shinya Masuda Prof. Dr. Tatsuya Tsukuda Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity ChemElectroChem Cluster compounds Gold Halides Luminescence Photoredox catalysis |
| title | Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity |
| title_full | Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity |
| title_fullStr | Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity |
| title_full_unstemmed | Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity |
| title_short | Introducing Iodide Ligands on IrAu12 Cluster Enhances Phosphorescence Efficiency and Photoredox Activity |
| title_sort | introducing iodide ligands on irau12 cluster enhances phosphorescence efficiency and photoredox activity |
| topic | Cluster compounds Gold Halides Luminescence Photoredox catalysis |
| url | https://doi.org/10.1002/celc.202300669 |
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