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How molecular architecture defines quantum yields

Pashley-Johnson, Fred; Munaweera, Rangika; Hossain, Sheikh I.; Gauci, Steven C. 1; Delafresnaye, Laura; Frisch, Hendrik; O’Mara, Megan L. ; Du Prez, Filip E. ; Barner-Kowollik, Christopher 1
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)

Abstract:

Understanding the intricate relationship between molecular architecture and function underpins most challenges at the forefront of chemical innovation. Bond-forming reactions are particularly influenced by the topology of a chemical structure, both on small molecule scale and in larger macromolecular frameworks. Herein, we elucidate the impact that molecular architecture has on the photo-induced cyclisations of a series of monodisperse macromolecules with defined spacers between photodimerisable moieties, and examine the relationship between propensity for intramolecular cyclisation and intermolecular network formation. We demonstrate a goldilocks zone of maximum reactivity between the sterically hindered and entropically limited regimes with a quantum yield of intramolecular cyclisation that is nearly an order of magnitude higher than the lowest value. As a result of the molecular design of trifunctional macromolecules, their quantum yields can be deconvoluted into the formation of two different cyclic isomers, as rationalised with molecular dynamics simulations. Critically, we visualise our solution-based studies with light-based additive manufacturing. ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000173364
Veröffentlicht am 13.08.2024
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2024
Sprache Englisch
Identifikator ISSN: 2041-1723
KITopen-ID: 1000173364
HGF-Programm 43.32.01 (POF IV, LK 01) Molecular Materials Basis for Optics & Photonics
Erschienen in Nature Communications
Verlag Nature Research
Band 15
Heft 1
Seiten Art.-Nr.: 6033
Vorab online veröffentlicht am 17.07.2024
Nachgewiesen in Web of Science
Dimensions
Scopus
Globale Ziele für nachhaltige Entwicklung Ziel 9 – Industrie, Innovation und Infrastruktur
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