大型芳香族光敏剂系间窜越时的基本电子变化：游离碱5,10,15,20-四（4-羧基苯基）卟啉
Fundamental electronic changes upon intersystem crossing in large aromatic photosensitizers: free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin.
作者信息
Büchner Robby, Vaz da Cruz Vinícius, Grover Nitika, Charisiadis Asterios, Fondell Mattis, Haverkamp Robert, Senge Mathias O, Föhlisch Alexander
机构信息
Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam, Germany.
Institute for Methods and Instrumentation for Synchrotron Radiation Research, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Str. 15, 12489, Berlin, Germany.
出版信息
Phys Chem Chem Phys. 2022 Mar 23;24(12):7505-7511. doi: 10.1039/d1cp05420a.
Free base 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin stands for the class of powerful porphyrin photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy in combination with time-dependent density functional theory (TD-DFT) gives direct access to the crucial excited molecular states within the unusual relaxation pathway. The efficient intersystem crossing, that is El-Sayed forbidden and not facilitated by a heavy atom is confirmed to be the result of the long singlet excited state lifetime (Q 4.9 ns) and thermal effects. Overall, the interplay of stabilization by conservation of angular momenta and vibronic relaxation drive the de-excitation in these chromophores.
游离碱5,10,15,20-四（4-羧基苯基）卟啉代表了用于单线态氧生成和光捕获的一类强大的卟啉光敏剂。动态紫外泵浦-N K边探针X射线吸收光谱与含时密度泛函理论（TD-DFT）相结合的原子水平选择性，能够直接获取异常弛豫途径中的关键激发分子态。高效的系间窜越，即El-Sayed禁阻且无重原子促进，被证实是长单线态激发态寿命（Q 4.9 ns）和热效应的结果。总体而言，角动量守恒引起的稳定作用与振动弛豫之间的相互作用驱动了这些发色团的去激发过程。
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