Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex
Abstract Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the de...
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Nature Portfolio
2025-01-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-025-01420-6 |
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| author | Yuichi Kitagawa Toranosuke Tomikawa Kota Aikawa Shiori Miyazaki Tomoko Akama Masato Kobayashi Mengfei Wang Sunao Shoji Koji Fushimi Kiyoshi Miyata Yuichi Hirai Takayuki Nakanishi Ken Onda Tetsuya Taketsugu Yasuchika Hasegawa |
| author_facet | Yuichi Kitagawa Toranosuke Tomikawa Kota Aikawa Shiori Miyazaki Tomoko Akama Masato Kobayashi Mengfei Wang Sunao Shoji Koji Fushimi Kiyoshi Miyata Yuichi Hirai Takayuki Nakanishi Ken Onda Tetsuya Taketsugu Yasuchika Hasegawa |
| author_sort | Yuichi Kitagawa |
| collection | DOAJ |
| description | Abstract Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the demonstration of CT emission from 4f- to π-orbitals using a trivalent europium (Eu(III)) complex, supported by both experimental and theoretical analyses. The Eu(III) complex exhibits an eight-coordination structure, comprising three anionic nitrates and two neutral electron-donating ligands containing a carbazole unit. The diffuse reflectance spectrum of the complex displays an absorption band at 440 nm and time-resolved emission analyses reveal a characteristic emission band at 550 nm. Comparative studies employing a trivalent gadolinium (Gd(III)) complex, alongside quantum chemical analyses, confirm that the observed absorption and emission bands are associated with CT transitions between π- and 4f-orbitals. The observation of CT emission based on the 4f-orbital offers novel insights into the field of molecular luminescence science and technology. |
| format | Article |
| id | doaj-art-cd5548234ea44359b5d94e9f40479e14 |
| institution | Kabale University |
| issn | 2399-3669 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Communications Chemistry |
| spelling | doaj-art-cd5548234ea44359b5d94e9f40479e142025-02-02T12:12:11ZengNature PortfolioCommunications Chemistry2399-36692025-01-01811610.1038/s42004-025-01420-6Charge transfer emission between π- and 4f-orbitals in a trivalent europium complexYuichi Kitagawa0Toranosuke Tomikawa1Kota Aikawa2Shiori Miyazaki3Tomoko Akama4Masato Kobayashi5Mengfei Wang6Sunao Shoji7Koji Fushimi8Kiyoshi Miyata9Yuichi Hirai10Takayuki Nakanishi11Ken Onda12Tetsuya Taketsugu13Yasuchika Hasegawa14Faculty of Engineering, Hokkaido UniversityGraduate School of Chemical Sciences and Engineering, Hokkaido UniversityGraduate School of Chemical Sciences and Engineering, Hokkaido UniversityDepartment of Chemistry, Kyushu UniversityInstitute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido UniversityInstitute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido UniversityInstitute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido UniversityFaculty of Engineering, Nara Women’s University, Kitauoya-NishimachiFaculty of Engineering, Hokkaido UniversityDepartment of Chemistry, Kyushu UniversityNational Institute for Materials ScienceNational Institute for Materials ScienceDepartment of Chemistry, Kyushu UniversityInstitute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido UniversityFaculty of Engineering, Hokkaido UniversityAbstract Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the demonstration of CT emission from 4f- to π-orbitals using a trivalent europium (Eu(III)) complex, supported by both experimental and theoretical analyses. The Eu(III) complex exhibits an eight-coordination structure, comprising three anionic nitrates and two neutral electron-donating ligands containing a carbazole unit. The diffuse reflectance spectrum of the complex displays an absorption band at 440 nm and time-resolved emission analyses reveal a characteristic emission band at 550 nm. Comparative studies employing a trivalent gadolinium (Gd(III)) complex, alongside quantum chemical analyses, confirm that the observed absorption and emission bands are associated with CT transitions between π- and 4f-orbitals. The observation of CT emission based on the 4f-orbital offers novel insights into the field of molecular luminescence science and technology.https://doi.org/10.1038/s42004-025-01420-6 |
| spellingShingle | Yuichi Kitagawa Toranosuke Tomikawa Kota Aikawa Shiori Miyazaki Tomoko Akama Masato Kobayashi Mengfei Wang Sunao Shoji Koji Fushimi Kiyoshi Miyata Yuichi Hirai Takayuki Nakanishi Ken Onda Tetsuya Taketsugu Yasuchika Hasegawa Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex Communications Chemistry |
| title | Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex |
| title_full | Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex |
| title_fullStr | Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex |
| title_full_unstemmed | Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex |
| title_short | Charge transfer emission between π- and 4f-orbitals in a trivalent europium complex |
| title_sort | charge transfer emission between π and 4f orbitals in a trivalent europium complex |
| url | https://doi.org/10.1038/s42004-025-01420-6 |
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