Jump to main content
Jump to site search
SCHEDULED MAINTENANCE Close the message box

Maintenance work is planned for Monday 16 August 2021 from 07:00 to 23:59 (BST).

Website performance may be temporarily affected and you may not be able to access some PDFs or images. If this does happen, refreshing your web browser should resolve the issue. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 12, 2020

Ultrafast photoinduced electron transfer in conjugated polyelectrolyte–acceptor ion pair complexes

Author affiliations

Abstract

Conjugated polyelectrolytes (CPEs) are a promising class of materials for photovoltaic and sensing applications due to their ability to undergo efficient photoinduced electron transfer (ET). Although water-soluble poly(p-phenylene ethynylene) (PPE) polyelectrolytes have been synthesized for various applications, no reports have clearly revealed the dynamics of the photoinduced ET process and charge transfer state of PPE-type CPE/electron acceptor systems. Herein, we investigated photoinduced ET from a water-soluble PPE based CPE functionalized with alkyl sulfonate (R–SO3) as side groups to three cationic electron acceptors. Steady-state absorption studies showed a bathochromic shift of the absorption band for all CPE/acceptor mixtures compared to CPE as a result of the suppression of the conformational changes in the polymer caused by the ion–pair interaction. Stern–Volmer (SV) fluorescence quenching studies revealed that all of the cationic electron acceptors efficiently quenched the fluorescence of CPE with SV constants (KSV) in excess of 106 M−1. Picosecond transient absorption (TA) studies of a CPE/methyl viologen mixture revealed the absorption feature of the cation radical state (CPE˙+) of the polyelectrolyte. Kinetic measurements established that the forward electron transfer in the polyelectrolyte/acceptor mixtures occurs with rate constant kf > 1 × 1012 s−1 and the return ET occurs with kb = 3 × 1011 s−1. We also demonstrated that the electron transfer between a PPE-type polyelectrolyte and an acceptor in their assemblies could be modulated by a supramolecular approach, which revealed that the nature of the acceptor–supramolecule host–guest complexes dictates the kinetics of the electron transfer process.

Graphical abstract: Ultrafast photoinduced electron transfer in conjugated polyelectrolyte–acceptor ion pair complexes

Supplementary files

Article information


Submitted
10 Jul 2020
Accepted
17 Sep 2020
First published
18 Sep 2020

Mater. Chem. Front., 2020,4, 3649-3659
Article type
Research Article

Ultrafast photoinduced electron transfer in conjugated polyelectrolyte–acceptor ion pair complexes

P. Jagadesan, S. R. Valandro and K. S. Schanze, Mater. Chem. Front., 2020, 4, 3649 DOI: 10.1039/D0QM00476F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements