The switchable phosphorescence and delayed fluorescence of a new rhodamine-like dye through allenylidene formation in a cyclometallated platinum(ii) system |
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Authors: | Shunan Zhao Yifan Zhu Ling Li Vronique Guerchais Julien Boixel Keith Man-Chung Wong |
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Institution: | School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 15001 China ; Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Blvd., Shenzhen 518055 P. R. China.; Univ Rennes, CNRS UMR6226, F-3500 Rennes France, |
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Abstract: | A new rhodamine-like alkyne-substituted ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. The chemo-induced “ON–OFF” switching capabilities on the spirolactone ring of the Rhodyne ligand with an end-capping platinum(ii) metal centre can modulate the interesting acetylide–allenylidene resonance. The long-lived 3IL excited state of Rhodyne in its ON state as an optically active opened form was revealed via steady-state and time-resolved spectroscopy studies. Exceptional near-infrared (NIR) phosphorescence and delayed fluorescence based on a rhodamine-like structure were observed at room temperature for the first time. The position of the alkyne communication bridge attached to the platinum(ii) unit was found to vary the lead(ii)-ion binding mode and also the possible resonance structure for metal-mediated allenylidene formation. The formation of a proposed allenylidene resonance structure was suggested to rationalize these phenomena.A new rhodamine-like ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. Allenylidene formation could trigger NIR phosphorescence at 740 nm originating from Rhodyne 3IL, as well as delayed fluorescence at 620 nm. |
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