Wang Zhijia, Toffoletti Antonio, Hou Yuqi, Zhao Jianzhang, Barbon Antonio, Dick Bernhard
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology E-208 West Campus, 2 Ling Gong Rd. Dalian 116024 China
Dipartimento di Scienze Chimiche, Università degli Studi di Padova Via Marzolo 1 35131 Padova Italy
Chem Sci. 2020 Dec 22;12(8):2829-2840. doi: 10.1039/d0sc05494a.
The triplet state lifetimes of organic chromophores are crucial for fundamental photochemistry studies as well as applications as photosensitizers in photocatalysis, photovoltaics, photodynamic therapy and photon upconversion. It is noteworthy that the triplet state lifetime of a chromophore can vary significantly for its analogues, while the exact reason was rarely studied. Herein with a few exemplars of typical BODIPY derivatives, which show triplet lifetimes varying up to 110-fold (1.4-160 μs), we found that for these derivatives with short triplet state lifetimes ( 1-3 μs), the electron spin polarization (ESP) pattern of the time-resolved electron paramagnetic resonance (TREPR) spectra of the triplet state is inverted at a longer delay time after laser pulse excitation, as a consequence of a strong anisotropy in the decay rates of the zero-field state sublevel of the triplet state. For the derivatives showing longer triplet state lifetimes (>50 μs), no such ESP inversion was observed. The observed fast decay of one sublevel is responsible for the short triplet state lifetime; theoretical computations indicate that it is due to a strong coupling between the T sublevel and the ground state mediated by the spin-orbit interaction. Another finding is that the heavy atom effect on the shortening of the triplet state lifetime is more significant for the T states with lower energy. To the best of our knowledge, this is the first systematic study to rationalize the short triplet state lifetime of visible-light-harvesting organic chromophores. Our results are useful for fundamental photochemistry and the design of photosensitizers showing long-lived triplet states.
有机发色团的三重态寿命对于基础光化学研究以及在光催化、光伏、光动力疗法和光子上转换中作为光敏剂的应用至关重要。值得注意的是,发色团的三重态寿命对于其类似物可能会有显著变化,而确切原因很少被研究。在此,以几种典型的BODIPY衍生物为例,它们的三重态寿命变化高达110倍(1.4 - 160微秒),我们发现对于这些三重态寿命较短(1 - 3微秒)的衍生物,在激光脉冲激发后的较长延迟时间,三重态的时间分辨电子顺磁共振(TREPR)光谱的电子自旋极化(ESP)模式会反转,这是由于三重态零场态子能级衰减率存在强烈各向异性的结果。对于三重态寿命较长(>50微秒)的衍生物,未观察到这种ESP反转。观察到的一个子能级的快速衰减导致了短的三重态寿命;理论计算表明这是由于自旋 - 轨道相互作用介导的T子能级与基态之间的强耦合。另一个发现是,重原子对三重态寿命缩短的影响对于能量较低的T态更为显著。据我们所知,这是首次对可见光捕获有机发色团短三重态寿命进行合理化的系统研究。我们的结果对于基础光化学以及设计具有长寿命三重态的光敏剂很有用。