How molecular architecture defines quantum yields.

Autor: Pashley-Johnson F; School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Polymer Chemistry Research Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281-S4, Ghent, 9000, Belgium., Munaweera R; Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Building 75, Cnr College Rd & Cooper Road, 4072, St Lucia, QLD, Australia., Hossain SI; Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Building 75, Cnr College Rd & Cooper Road, 4072, St Lucia, QLD, Australia., Gauci SC; School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Delafresnaye L; School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia., Frisch H; School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia.; Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia., O'Mara ML; Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Building 75, Cnr College Rd & Cooper Road, 4072, St Lucia, QLD, Australia. m.omara@uq.edu.au., Du Prez FE; Polymer Chemistry Research Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281-S4, Ghent, 9000, Belgium. filip.duprez@ugent.be., Barner-Kowollik C; School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia. christopher.barnerkowollik@qut.edu.au.; Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, 4000, Brisbane, QLD, Australia. christopher.barnerkowollik@qut.edu.au.; Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany. christopher.barnerkowollik@qut.edu.au.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2024 Jul 17; Vol. 15 (1), pp. 6033. Date of Electronic Publication: 2024 Jul 17.
DOI: 10.1038/s41467-024-50366-1
Abstrakt: 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. We formulate four photoresists for microprinting, revealing that the precise positioning of functional groups is critical for resist performance, with lower intramolecular quantum yields leading to higher-quality printing in most cases.
(© 2024. The Author(s).)
Databáze: MEDLINE
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