Premium
Photochemistry of a 9‐Dithianyl‐Pyronin Derivative: A Cornucopia of Reaction Intermediates Lead to Common Photoproducts
Author(s) -
Martínek Marek,
Váňa Jiří,
Šebej Peter,
Navrátil Rafael,
Slanina Tomáš,
Ludvíková Lucie,
Roithová Jana,
Klán Petr
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000370
Subject(s) - chemistry , xanthene , photochemistry , derivative (finance) , formic acid , mass spectrometry , organic chemistry , financial economics , economics , chromatography
Leaving groups attached to the meso ‐methyl position of many common dyes, such as xanthene, BODIPY, or pyronin derivatives, can be liberated upon irradiation with visible light. However, the course of phototransformations of such photoactivatable systems can be quite complex and the identification of reaction intermediates or even products is often neglected. This paper exemplifies the photochemistry of a 9‐dithianyl‐pyronin derivative, which undergoes an oxidative transformation at the meso ‐position to give a 3,6‐diamino‐9 H ‐xanthen‐9‐one derivative, formic acid, and carbon monoxide as the main photoproducts. The course of this multi‐photon multi‐step reaction was studied under various conditions by steady‐state and time‐resolved optical spectroscopy, mass spectrometry and NMR spectroscopy to understand the effects of solvents and molecular oxygen on individual steps. Our analyses have revealed the existence of many intermediates and their interrelationships to provide a complete picture of the transformation, which can bring new inputs to a rational design of new photoactivatable pyronin or xanthene derivatives.