[en] H-bonded N-heterotriangulene (NHT) supramolecular polymers offer a nice playground to explore the nature and dynamics of electronic excitations in low-dimensional organic nanostructures. Here, we report on a comprehensive molecular modeling of the excited-state electronic structure and optical properties of model NHT stacks, highlighting the important role of intermolecular charge-transfer (CT) excitations in shaping their optical absorption and emission lineshapes. Most importantly, we show that the coupling between the local and CT excitations, modulated by the electric fields induced by the presence of polar amide groups forming H-bonded arrays along the stacks, significantly increases the resulting hybrid exciton bandwidth. We discuss these findings in the context of the efficient transport of singlet excitons over the μm length scale reported experimentally on individual self-assembled nanofibers with molecular-scale diameter.
Disciplines :
Chemistry
Author, co-author :
Cerdá, Jesús ; Laboratory for Chemistry of Novel Materials, University of Mons, Mons 7000, Belgium
Ortí, Enrique ; Instituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, Paterna 46980, Spain
Beljonne, David ; Université de Mons - UMONS > Faculté des Sciences > Service de Chimie des matériaux nouveaux
Aragó, Juan ; Instituto de Ciencia Molecular (ICMol), Universitat de València, Catedrático José Beltrán 2, Paterna 46980, Spain
Language :
English
Title :
Optical Properties of H-Bonded Heterotriangulene Supramolecular Polymers: Charge-Transfer Excitations Matter.
R400 - Institut de Recherche en Science et Ingénierie des Matériaux R150 - Institut de Recherche sur les Systèmes Complexes
Funders :
Conselleria d'Educació, Cultura i Esport EC - European Commission Ministerio de Ciencia e Innovacion FEDER - Fonds Européen de Développement Régional HORIZON EUROPE Marie Sklodowska-Curie Actions F.R.S.-FNRS - Fonds de la Recherche Scientifique
Funding text :
Financial support by the MCIN/AEI of Spain (projects CNS2022-135187, PID2021-128569NB-I00, TED2021-131255B\u2013C44 and CEX2019-000919-M, funded by MCIN/AEI/10.13039/501100011033, \u201CERDF A way of making Europe\u201D, and \u201CEuropean Union NextGenerationEU/PRTR\u201D) and the Generalitat Valenciana (MFA/2022/017) is acknowledged. The MFA/2022/017 project forms part of the Advanced Materials program supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana. Research in Mons is supported by the Belgian National Fund for Scientific Research (FRS-FNRS) within the Consortium des E\u0301quipements de Calcul Intensif \u2013 CE\u0301CI (grant number U.G.018.18), and by the Walloon Region (LUCIA Tier-1 supercomputer; grant number 1910247). D.B. is a FNRS research director. J.C. acknowledges to European Union for his Marie Curie Individual fellowship (HORIZON-MSCA-2022-PF-01-01, project n\u00B0 101106941).
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