How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?
How does tautomerization affect the excited-state dynamics of an amino acid-derivatized corrole?
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DOI：
10.1007/s11120-021-00824-4
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发表时间：
2021-05
影响因子：
3.7
通讯作者：
Vullev VI
中科院分区：
文献类型：
--
作者：
Clark JA;Orłowski R;Derr JB;Espinoza EM;Gryko DT;Vullev VI
在二十一世纪的前二十年，corrole作为一类重要的卟啉类化合物出现在光子学和生物医学光子学领域。与卟啉相比，corrol具有较低的分子对称性和较高的电子密度，从而具有独特的互补性质。例如，在自由碱的大环中，3个质子分布在4个吡咯氮中。它产生了具有不同热力学能的不同的互变异构体。在这里，我们关注的是l-苯丙氨酸修饰的分子的激发态动力学。单线激发态的互变异构化发生在10-100皮秒的时间尺度上，并表现出明显的动力学同位素效应。然而，它并没有明显影响纳秒灭活的光激发和它的基本光物理。然而，考虑到激发态互变异构体之间100 mev的能量差异，这种激发态互变异构动力学可以强烈地影响具有可比或更短时间尺度的光诱导过程。在达到激发态互变体种群的平衡热化之前，对电荷转移和能量转移动力学的影响确实是实质性的。这些考虑在设计人工光合作用和其他形式的能量转换和电荷转导系统时至关重要。在线版本包含补充材料，可在10.1007/s11120-021-00824-4获得。
In the first two decades of the XXI century, corroles have emerged as an important class of porphyrinoids for photonics and biomedical photonics. In comparison with porphyrins, corroles have lower molecular symmetry and higher electron density, which leads to uniquely complementary properties. In macrocycles of free-base corroles, for example, three protons are distributed among four pyrrole nitrogens. It results in distinct tautomers that have different thermodynamic energies. Herein, we focus on the excited-state dynamics of a corrole modified with l-phenylalanine. The tautomerization in the singlet-excited state occurs in the timescales of about 10–100 picoseconds and exhibits substantial kinetic isotope effects. It, however, does not discernably affect nanosecond deactivation of the photoexcited corrole and its basic photophysics. Nevertheless, this excited-state tautomerization dynamics can strongly affect photoinduced processes with comparable or shorter timescales, considering the 100-meV energy differences between the tautomers in the excited state. The effects on the kinetics of charge transfer and energy transfer, initiated prior to reaching the equilibrium thermalization of the excited-state tautomer population, can be indeed substantial. Such considerations are crucially important in the design of systems for artificial photosynthesis and other forms of energy conversion and charge transduction. The online version contains supplementary material available at 10.1007/s11120-021-00824-4.
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2.8
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DOI：
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