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.

在二十一世纪的前二十年，corroles 已成为光子学和生物医学光子学中一类重要的卟啉类化合物。与卟啉相比，corroles具有较低的分子对称性和较高的电子密度，这导致了独特的互补性质。例如，在游离碱氯的大环中，三个质子分布在四个吡咯氮中。它导致具有不同热力学能量的不同互变异构体。在这里，我们专注于用l修饰的 corrole 的激发态动力学-苯丙氨酸。单重激发态的互变异构发生在大约 10-100 皮秒的时间尺度内，并表现出显着的动力学同位素效应。然而，它不会明显影响光激发的 corrole 及其基本光物理学的纳秒失活。然而，考虑到处于激发态的互变异构体之间存在 100-meV 的能量差异，这种激发态互变异构化动力学可以强烈影响具有相当或更短时间尺度的光诱导过程。在达到激发态互变异构体群的平衡热化之前开始的对电荷转移和能量转移动力学的影响可能确实很大。