Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function

Henry E Symons; Maximilian J L Hagemann; Robert L Harniman; Charl F J Faul

doi:10.1039/D1TC04518K

Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function

Henry E Symons, Maximilian J L Hagemann, Robert L Harniman, Charl F J Faul^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

13 Citations (Scopus)

Abstract

Controlling the self-assembly of functional organic molecules provides opportunities to optimise the interlinked properties and structures of these materials for specific applications. Perylene diimide (PDI) derivative, PDI1, was used as a model monomer to investigate the effects of heteroatom substitution in supramolecular polymer systems. In addition to the previously reported optoelectronic effects (including shifted absorbance and quenched fluorescence), thionation was found to have a significant impact on the self-assembly behaviour of PDI1. The thionated analogues of this species displayed a diverse range of self-assembled morphologies, rationalised through changes in intermolecular interactions. Furthermore, thionation results in a transition from highly cooperative to isodesmic assembly mechanism. Such mechanistic control should also be applicable to many other supramolecular systems based on either hydrogen-bonding or π-stacking interactions, and presents an important route for the regulation of dynamic polymer properties. Finally, thionation was found to result in a substantial increase in conductivity recorded within analogous supramolecular polymer structures.

Original language	English
Pages (from-to)	2828-2837
Number of pages	10
Journal	Journal of Materials Chemistry C
Volume	10
Issue number	7
DOIs	https://doi.org/10.1039/D1TC04518K
Publication status	Published - 24 Jan 2022

Bibliographical note

Funding Information:
H. E. S. acknowledges the EPSRC for support (EP/N509619/1). M. J. L. H. acknowledges the EPSRC for support (EP/R513179/1). Mass spectrometric measurements were performed using instrumentation bought through the Core Capability for Chemistry Research—Strategic Investment in Mass Spectrometry EPSRC grant (EP/K03927X/1). AFM, EFM and PF-TUNA measurements were conducted in the Chemical Imaging Facility, School of Chemistry, University of Bristol with equipment funded by EPSRC under ‘‘Atoms to Applications’’ Grant EP/K035746/1. All authors thank the School of Chemistry for research support.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

Research Groups and Themes

Inorganic & Materials

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Controlling Interactions and Functionality of PDI-Based Compounds by Targeted Chemical Modification
Hagemann, M. J. L. (Author), Faul, C. F. (Supervisor), 23 Aug 2024
Student thesis: Doctoral Thesis › Doctor of Philosophy (PhD)

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title = "Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function",

abstract = "Controlling the self-assembly of functional organic molecules provides opportunities to optimise the interlinked properties and structures of these materials for specific applications. Perylene diimide (PDI) derivative, PDI1, was used as a model monomer to investigate the effects of heteroatom substitution in supramolecular polymer systems. In addition to the previously reported optoelectronic effects (including shifted absorbance and quenched fluorescence), thionation was found to have a significant impact on the self-assembly behaviour of PDI1. The thionated analogues of this species displayed a diverse range of self-assembled morphologies, rationalised through changes in intermolecular interactions. Furthermore, thionation results in a transition from highly cooperative to isodesmic assembly mechanism. Such mechanistic control should also be applicable to many other supramolecular systems based on either hydrogen-bonding or π-stacking interactions, and presents an important route for the regulation of dynamic polymer properties. Finally, thionation was found to result in a substantial increase in conductivity recorded within analogous supramolecular polymer structures. ",

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note = "Funding Information: H. E. S. acknowledges the EPSRC for support (EP/N509619/1). M. J. L. H. acknowledges the EPSRC for support (EP/R513179/1). Mass spectrometric measurements were performed using instrumentation bought through the Core Capability for Chemistry Research—Strategic Investment in Mass Spectrometry EPSRC grant (EP/K03927X/1). AFM, EFM and PF-TUNA measurements were conducted in the Chemical Imaging Facility, School of Chemistry, University of Bristol with equipment funded by EPSRC under {\textquoteleft}{\textquoteleft}Atoms to Applications{\textquoteright}{\textquoteright} Grant EP/K035746/1. All authors thank the School of Chemistry for research support. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

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AU - Faul, Charl F J

N1 - Funding Information: H. E. S. acknowledges the EPSRC for support (EP/N509619/1). M. J. L. H. acknowledges the EPSRC for support (EP/R513179/1). Mass spectrometric measurements were performed using instrumentation bought through the Core Capability for Chemistry Research—Strategic Investment in Mass Spectrometry EPSRC grant (EP/K03927X/1). AFM, EFM and PF-TUNA measurements were conducted in the Chemical Imaging Facility, School of Chemistry, University of Bristol with equipment funded by EPSRC under ‘‘Atoms to Applications’’ Grant EP/K035746/1. All authors thank the School of Chemistry for research support. Publisher Copyright: © 2022 The Royal Society of Chemistry.

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N2 - Controlling the self-assembly of functional organic molecules provides opportunities to optimise the interlinked properties and structures of these materials for specific applications. Perylene diimide (PDI) derivative, PDI1, was used as a model monomer to investigate the effects of heteroatom substitution in supramolecular polymer systems. In addition to the previously reported optoelectronic effects (including shifted absorbance and quenched fluorescence), thionation was found to have a significant impact on the self-assembly behaviour of PDI1. The thionated analogues of this species displayed a diverse range of self-assembled morphologies, rationalised through changes in intermolecular interactions. Furthermore, thionation results in a transition from highly cooperative to isodesmic assembly mechanism. Such mechanistic control should also be applicable to many other supramolecular systems based on either hydrogen-bonding or π-stacking interactions, and presents an important route for the regulation of dynamic polymer properties. Finally, thionation was found to result in a substantial increase in conductivity recorded within analogous supramolecular polymer structures.

AB - Controlling the self-assembly of functional organic molecules provides opportunities to optimise the interlinked properties and structures of these materials for specific applications. Perylene diimide (PDI) derivative, PDI1, was used as a model monomer to investigate the effects of heteroatom substitution in supramolecular polymer systems. In addition to the previously reported optoelectronic effects (including shifted absorbance and quenched fluorescence), thionation was found to have a significant impact on the self-assembly behaviour of PDI1. The thionated analogues of this species displayed a diverse range of self-assembled morphologies, rationalised through changes in intermolecular interactions. Furthermore, thionation results in a transition from highly cooperative to isodesmic assembly mechanism. Such mechanistic control should also be applicable to many other supramolecular systems based on either hydrogen-bonding or π-stacking interactions, and presents an important route for the regulation of dynamic polymer properties. Finally, thionation was found to result in a substantial increase in conductivity recorded within analogous supramolecular polymer structures.

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DO - 10.1039/D1TC04518K

M3 - Article (Academic Journal)

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JO - Journal of Materials Chemistry C

JF - Journal of Materials Chemistry C

IS - 7

ER -

Thionated PDI supramolecular polymers: controlling aggregation mechanisms, morphology and function

Abstract

Bibliographical note

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Student theses

Controlling Interactions and Functionality of PDI-Based Compounds by Targeted Chemical Modification

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