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Inactivation of Competitive Decay Channels Leads to Enhanced Coumarin Photochemistry
Author(s) -
Klimek Robin,
Asido Marvin,
Hermanns Volker,
Junek Stephan,
Wachtveitl Josef,
Heckel Alexander
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200647
Subject(s) - photochemistry , fluorophore , chromophore , chemistry , intramolecular force , coumarin , photodissociation , fluorescence , stereochemistry , organic chemistry , physics , quantum mechanics
Abstract In the development of photolabile protecting groups, it is of high interest to selectively modify photochemical properties with structural changes as simple as possible. In this work, knowledge of fluorophore optimization was adopted and used to design new coumarin‐ based photocages. Photolysis efficiency was selectively modulated by inactivating competitive decay channels, such as twisted intramolecular charge transfer (TICT) or hydrogen‐bonding, and the photolytic release of the neurotransmitter serotonin was demonstrated. Structural modifications inspired by the fluorophore ATTO 390 led to a significant increase in the uncaging cross section that can be further improved by the simple addition of a double bond. Ultrafast transient absorption spectroscopy gave insights into the underlying solvent‐dependent photophysical dynamics. The chromophores presented here are excellently suited as new photocages in the visible wavelength range due to their simple synthesis and their superior photochemical properties.