Rethinking Uncaging: A New Antiaromatic Photocage Driven by a Gain of Resonance Energy.
Baird's rule
excited state aromaticity
photochemistry
photolabile protecting groups
substituent effects
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
07 Oct 2021
07 Oct 2021
Historique:
received:
30
06
2021
pubmed:
8
8
2021
medline:
8
8
2021
entrez:
7
8
2021
Statut:
ppublish
Résumé
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
Identifiants
pubmed: 34363415
doi: 10.1002/chem.202102351
pmc: PMC8519059
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
14121-14127Subventions
Organisme : deutsche forschungsgemeinschaft
ID : GRK 1886
Informations de copyright
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
Références
J Am Chem Soc. 2017 Oct 25;139(42):15168-15175
pubmed: 29039200
J Am Chem Soc. 2020 Jun 24;142(25):10942-10954
pubmed: 32456426
Chemistry. 2018 Sep 3;24(49):13026-13035
pubmed: 29889321
Chem Rev. 2014 May 28;114(10):5379-425
pubmed: 24712859
Chem Sci. 2016 Jan 1;7(1):655-665
pubmed: 29896352
J Am Chem Soc. 2014 Jun 25;136(25):8933-40
pubmed: 24911243
Chem Sci. 2017 Oct 31;9(2):387-391
pubmed: 29629108
J Org Chem. 2020 Oct 16;85(20):13015-13028
pubmed: 33003699
Phys Chem Chem Phys. 2020 Jun 28;22(24):13418-13430
pubmed: 32515438
Phys Chem Chem Phys. 2005 Sep 21;7(18):3297-305
pubmed: 16240044
J Phys Chem A. 2008 Aug 7;112(31):7303-9
pubmed: 18636691
Chem Sci. 2018 Feb 9;9(10):2797-2802
pubmed: 29732066
Nat Commun. 2020 Feb 7;11(1):793
pubmed: 32034152
Chem Rev. 2005 Oct;105(10):3842-88
pubmed: 16218569
Nat Commun. 2020 Apr 21;11(1):1925
pubmed: 32317631
Angew Chem Int Ed Engl. 2018 Mar 5;57(11):2768-2798
pubmed: 28521066
Angew Chem Int Ed Engl. 2013 Dec 16;52(51):13558-61
pubmed: 24174377
Chemistry. 2021 Oct 7;27(56):14121-14127
pubmed: 34363415
J Chem Phys. 2010 Dec 28;133(24):244111
pubmed: 21197980
J Am Chem Soc. 2003 Jul 16;125(28):8546-54
pubmed: 12848562
Angew Chem Int Ed Engl. 2016 Jul 25;55(31):8948-52
pubmed: 27294300
J Phys Chem A. 2008 Dec 11;112(49):12707-13
pubmed: 19007145
Chemistry. 2001 Apr 17;7(8):1808-15
pubmed: 11349923
Chem Commun (Camb). 2012 Mar 14;48(22):2746-8
pubmed: 22159276
Chem Rev. 2020 Dec 23;120(24):13135-13272
pubmed: 33125209
Chemistry. 2021 Jan 26;27(6):2212-2218
pubmed: 32955154
Photochem Photobiol Sci. 2011 Jun;10(6):920-30
pubmed: 21311798