Zhao Shunan, Zhu Yifan, Li Ling, Guerchais Véronique, Boixel Julien, Wong Keith Man-Chung
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
Chem Sci. 2021 Jul 7;12(33):11056-11064. doi: 10.1039/d1sc02787e. eCollection 2021 Aug 25.
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 IL excited state of Rhodyne in its ON state as an optically active opened form was revealed 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.
设计了一种新型的类罗丹明炔基取代配体（Rhodyne），用于配位环金属化铂（II）体系。Rhodyne配体的螺内酯环上的化学诱导“开-关”切换能力与封端的铂（II）金属中心可以调节有趣的乙炔基-亚联烯基共振。通过稳态和时间分辨光谱研究揭示了Rhodyne处于“开”状态时作为光学活性开放形式的长寿命IL激发态。首次在室温下观察到基于类罗丹明结构的异常近红外（NIR）磷光和延迟荧光。发现连接到铂（II）单元的炔基通讯桥的位置会改变铅（II）离子的结合模式以及金属介导的亚联烯基形成的可能共振结构。提出了一种亚联烯基共振结构的形成，以合理解释这些现象。
