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Interplay Between J‐ and H‐Type Coupling in Aggregates of π‐Conjugated Polymers: A Single‐Molecule Perspective
Author(s) -
Eder Theresa,
Vogelsang Jan,
Bange Sebastian,
Remmerssen Klaas,
Schmitz Daniela,
Jester StefanS.,
Keller Tristan J.,
Höger Sigurd,
Lupton John M.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912374
Subject(s) - conjugated system , chromophore , excited state , coupling (piping) , monomer , dipole , chemical physics , molecule , superposition principle , polymer , chemistry , type (biology) , spectral line , molecular physics , materials science , atomic physics , photochemistry , physics , quantum mechanics , organic chemistry , ecology , metallurgy , biology
Abstract Strong dipole–dipole coupling within and between π‐conjugated segments shifts electronic transitions, and modifies vibronic coupling and excited‐state lifetimes. Since J‐type coupling between monomers along the conjugated‐polymer (CP) chain and H‐type coupling of chromophores between chains of a CP compete, a superposition of the spectral modifications arising from each type of coupling emerges, making the two couplings hard to discern in the ensemble. We introduce a single‐molecule H‐type aggregate of fixed spacing and variable length of up to 10 nm. HJ‐type aggregate formation is visualized intuitively in the scatter of single‐molecule spectra.