TY  - JOUR
A1  - Hermanns, Volker
A1  - Scheurer, Maximilian
A1  - Kersten, Nils Frederik
A1  - Abdellaoui, Chahinez
A1  - Wachtveitl, Josef
A1  - Dreuw, Andreas
A1  - Heckel, Alexander
T1  - Rethinking uncaging: a new antiaromatic photocage driven by a gain of resonance energy
T2  - Chemistry - a European journal
N2  - Photoactivatable compounds for example photoswitches or photolabile protecting groups (PPGs, photocages) for spatiotemporal light control, play a crucial role in different areas of research. For each application, parameters such as the absorption spectrum, solubility in the respective media and/or photochemical quantum yields for several competing processes need to be optimized. The design of new photochemical tools therefore remains an important task. In this study, we exploited the concept of excited-state-aromaticity, first described by N. Colin Baird in 1971, to investigate a new class of photocages, based on cyclic, ground-state-antiaromatic systems. Several thio- and nitrogen-functionalized compounds were synthesized, photochemically characterized and further optimized, supported by quantum chemical calculations. After choosing the optimal scaffold, which shows an excellent uncaging quantum yield of 28 %, we achieved a bathochromic shift of over 100 nm, resulting in a robust, well accessible, visible light absorbing, compact new photocage with a clean photoreaction and a high quantum product (ϵ⋅Φ) of 893 M−1 cm−1 at 405 nm.
KW  - Baird's rule
KW  - excited state aromaticity
KW  - photochemistry
KW  - photolabile protecting groups
KW  - substituent effects
Y1  - 2021
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/62650
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-626506
SN  - 1521-3765
N1  - Deutsche Forschungsgemeinschaft. Grant Number: GRK 1886. Open access funding enabled and organized by Projekt DEAL.
N1  - Early View: Online Version before inclusion in an issue
N1  - Version of Record: http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:hebis:30:3-644951
VL  - 27
IS  - online version before inclusion in an issue
SP  - 1
EP  - 8
PB  - Wiley-VCH
CY  - Weinheim
ER  -