Refereed journal article or data article (A1)

J-like aggregation of a cationic polythiophene with hydrogen-bonding capabilities due to 1,4-dioxane: Solution excitation spectra and fluorescence, morphology and surface free energy of films




List of AuthorsDomínguez Sergio E, Vuolle Antti, Butler-Hallissey Ciarán, Ääritalo Timo, Damlin Pia, Kvarnström Carita

PublisherElsevier Inc.

Publication year2021

JournalJournal of Colloid and Interface Science

Journal name in sourceJournal of colloid and interface science

Journal acronymJ Colloid Interface Sci

Volume number584

Start page281

End page294

Number of pages14

ISSN0021-9797

eISSN1095-7103

DOIhttp://dx.doi.org/10.1016/j.jcis.2020.09.124

URLhttps://doi.org/10.1016/j.jcis.2020.09.124

Self-archived copy’s web addresshttps://research.utu.fi/converis/portal/detail/Publication/49843762


Abstract
This work presents solution- and solid-state evidence of the enhancement of J-like aggregation of a cationic polythiophene (CPT) with isothiouronium functionalities (PT1), caused by a decrease in the polarity and hydrogen-bonding (H-bonding) capacity of the solvent, generated by using a 50:50 v/v 1,4-dioxane-water mixture (W-DI) instead of water. In solution, the presence of 1,4-dioxane (DI) seems to generate selective solvation, tuning the energy transfer within PT1 from inter-chain into intra-chain, enhancing J-like aggregation. On the other hand, during the casting process, the presence of DI directs the interaction with solid-substrates, generating an increase in the solid-state fluorescence, modifying the morphology from one similar to ballistic-aggregation (BA) into one similar to attachment limited aggregation (ALA), DI also modifies the SFE by increasing slightly its polar contribution (γSp) and decreasing the dispersive one (γSd). These results can be explained to be caused by a "coating" effect in presence of DI (as proposed before experimentally and computationally). Our results show a clear correlation between the solution- and solid-state properties of PT1 in each solvent, further validating the use of the fluorescence excitation spectra to trace J-like aggregation of water-soluble conjugated polymeric fluorophores in solution. This information could be useful for predicting and designing specific mesoscopic architectures of CPTs (and conjugated polyelectrolytes in general), which are molecules lacking of clear structure-function guidelines for designing high-performance polythiophene-based interlayer materials, especially for CPTs (and conjugated polyelectrolytes (CPEs) in general), particularly those with H-bonding capabilities. To the best of our knowledge the use of solution-state fluorescence excitation spectra to identify J-like aggregation of water-soluble conjugated polymers (CPs) has been scarcely used/discussed in literature and no correlation with solid-state properties was reported previously.

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Last updated on 2022-12-10 at 14:32