Thor Waygen, Wu Yue, Wang Lei, Zhang Yonghong, Tanner Peter A, Wong Ka-Leung
Department of Chemistry, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong SAR.
State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education & Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, College of Chemistry, Xinjiang University, Urumqi, 830046, Xinjiang, PR China.
Nat Commun. 2021 Nov 11;12(1):6532. doi: 10.1038/s41467-021-26927-z.
Emission from the triplet state of an organo-lanthanide complex is observed only when the energy transfer to the lanthanide ion is absent. The triplet state lifetime under cryogenic conditions for organo-lanthanide compounds usually ranges up to tens of milliseconds. The compound LaL1(TTA) reported herein exhibits 77 K phosphorescence observable by the naked eye for up to 30 s. Optical spectroscopy, density functional theory (DFT) and time-dependent DFT techniques have been applied to investigate the photophysical processes of this compound. In particular, on-off continuous irradiation cycles reveal a charging behaviour of the emission which is associated with triplet-triplet absorption because it shows a shorter rise lifetime than the corresponding decay lifetime and it varies with illumination intensity. The discovery of the behaviour of this compound provides insight into important photophysical processes of the triplet state of organo-lanthanide systems and may open new fields of application such as data encryption, anti-counterfeiting and temperature switching.
只有在不存在向镧系离子的能量转移时,才会观察到有机镧系配合物三重态的发射。有机镧系化合物在低温条件下的三重态寿命通常长达几十毫秒。本文报道的化合物LaL1(TTA)在77 K时呈现肉眼可观察到的磷光,持续时间长达30秒。已应用光谱学、密度泛函理论(DFT)和含时DFT技术来研究该化合物的光物理过程。特别是,开-关连续辐照循环揭示了发射的充电行为,这与三重态-三重态吸收有关,因为它的上升寿命比相应的衰减寿命短,并且随光照强度而变化。该化合物这一行为的发现为了解有机镧系体系三重态的重要光物理过程提供了见解,并可能开辟数据加密、防伪和温度切换等新的应用领域。