Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond
Abstract In contrast to the extensively studied dirhodium(II) complexes and iridium(III) complexes, neutral or dicationic dinuclear iridium(II) complexes with an unsupported ligand are underdeveloped. Here, a series of tetracationic dinuclear iridium(II) complexes, featuring the unsupported Ir(II)–I...
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Nature Portfolio
2022-11-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-022-00775-4 |
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| author | Fangrui Zheng Yuhong Yang Siye Wu Shunan Zhao Yifan Zhu Huimin Su Jun-Feng Dai Zeyin Yan Lung Wa Chung Keith Man-Chung Wong |
| author_facet | Fangrui Zheng Yuhong Yang Siye Wu Shunan Zhao Yifan Zhu Huimin Su Jun-Feng Dai Zeyin Yan Lung Wa Chung Keith Man-Chung Wong |
| author_sort | Fangrui Zheng |
| collection | DOAJ |
| description | Abstract In contrast to the extensively studied dirhodium(II) complexes and iridium(III) complexes, neutral or dicationic dinuclear iridium(II) complexes with an unsupported ligand are underdeveloped. Here, a series of tetracationic dinuclear iridium(II) complexes, featuring the unsupported Ir(II)–Ir(II) single bond with long bond distances (2.8942(4)–2.9731(4) Å), are synthesized and structurally characterized. Interestingly, compared to the previous unsupported neutral or dicationic diiridium(II) complexes, our DFT and high-level DLPNO-CCSD(T) results found the largest binding energy in these tetracationic complexes even with the long Ir(II)–Ir(II) bond. Our study further reveals that London dispersion interactions enhance the stability cooperatively and significantly to overcome the strong electrostatic repulsion between two half dicationic metal fragments. This class of complexes also exhibit photoluminescence in solution and solid states, which, to our knowledge, represents the first example of this unsupported dinuclear iridium(II) system. In addition, their photoreactivity involving the generation of iridium(II) radical monomer from homolytic cleavage was also explored. The experimental results of photophysical and photochemical behaviours were also correlated with computational studies. |
| format | Article |
| id | doaj-art-d4bfcc4a18394d39bb5c1a2c06d7f37d |
| institution | DOAJ |
| issn | 2399-3669 |
| language | English |
| publishDate | 2022-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Communications Chemistry |
| spelling | doaj-art-d4bfcc4a18394d39bb5c1a2c06d7f37d2025-08-20T03:10:18ZengNature PortfolioCommunications Chemistry2399-36692022-11-015111210.1038/s42004-022-00775-4Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bondFangrui Zheng0Yuhong Yang1Siye Wu2Shunan Zhao3Yifan Zhu4Huimin Su5Jun-Feng Dai6Zeyin Yan7Lung Wa Chung8Keith Man-Chung Wong9Department of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyShenzhen Institute for Quantum Science and Engineering, Southern University of Science and Technology, International Quantum Academy (SIQA), and Shenzhen Branch, Hefei National Laboratory, Shenzhen Key Laboratory of Quantum Science and EngineeringShenzhen Institute for Quantum Science and Engineering, Southern University of Science and Technology, International Quantum Academy (SIQA), and Shenzhen Branch, Hefei National Laboratory, Shenzhen Key Laboratory of Quantum Science and EngineeringDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyDepartment of Chemistry, Southern University of Science and TechnologyAbstract In contrast to the extensively studied dirhodium(II) complexes and iridium(III) complexes, neutral or dicationic dinuclear iridium(II) complexes with an unsupported ligand are underdeveloped. Here, a series of tetracationic dinuclear iridium(II) complexes, featuring the unsupported Ir(II)–Ir(II) single bond with long bond distances (2.8942(4)–2.9731(4) Å), are synthesized and structurally characterized. Interestingly, compared to the previous unsupported neutral or dicationic diiridium(II) complexes, our DFT and high-level DLPNO-CCSD(T) results found the largest binding energy in these tetracationic complexes even with the long Ir(II)–Ir(II) bond. Our study further reveals that London dispersion interactions enhance the stability cooperatively and significantly to overcome the strong electrostatic repulsion between two half dicationic metal fragments. This class of complexes also exhibit photoluminescence in solution and solid states, which, to our knowledge, represents the first example of this unsupported dinuclear iridium(II) system. In addition, their photoreactivity involving the generation of iridium(II) radical monomer from homolytic cleavage was also explored. The experimental results of photophysical and photochemical behaviours were also correlated with computational studies.https://doi.org/10.1038/s42004-022-00775-4 |
| spellingShingle | Fangrui Zheng Yuhong Yang Siye Wu Shunan Zhao Yifan Zhu Huimin Su Jun-Feng Dai Zeyin Yan Lung Wa Chung Keith Man-Chung Wong Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond Communications Chemistry |
| title | Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond |
| title_full | Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond |
| title_fullStr | Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond |
| title_full_unstemmed | Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond |
| title_short | Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond |
| title_sort | structure property relationships of photofunctional diiridium ii complexes with tetracationic charge and an unsupported ir ir bond |
| url | https://doi.org/10.1038/s42004-022-00775-4 |
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