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[2.2.2.2]Paracyclophanetetraenes (PCTs): cyclic structural analogues of poly(p‑phenylene vinylene)s (PPVs)

Title: [2.2.2.2]Paracyclophanetetraenes (PCTs): cyclic structural analogues of poly(p‑phenylene vinylene)s (PPVs)
Authors: Pletzer, M
Plasser, F
Rimmele, M
Heeney, M
Glöcklhofer, F
Item Type: Working Paper
Abstract: Background: Poly(p-phenylene vinylene)s (PPVs) and [2.2.2.2]paracyclophanetetraene (PCT) are both composed of alternating π-conjugated para-phenylene and vinylene units. However, while the former constitute a class of π-conjugated polymers that has been used in organic electronics for decades, the latter is a macrocycle that only recently revealed its potential for applications such as organic battery electrodes. The cyclic structure endows PCT with unusual properties, and further tuning of these may be required for specific applications. Methods: In this article, we adopt an approach often used for tuning the properties of PPVs, the introduction of alkoxy (or alkylthio) substituents at the phenylene units, for tuning the optoelectronic properties of PCT. The resulting methoxy- and methylthio-substituted PCTs, obtained by Wittig cyclisation reactions, are studied by UV-vis absorption, photoluminescence, and cyclic voltammetry measurements, and investigated computationally using the visualisation of chemical shielding tensors (VIST) method. Results: The measurements show that substitution leads to slight changes in terms of absorption/emission energies and redox potentials while having a pronounced effect on the photoluminescence intensity. The computations show the effect of the substituents on the ring currents and chemical shielding and on the associated local and global (anti)aromaticity of the macrocycles, highlighting the interplay of local and global aromaticity in various electronic states. Conclusions: The study offers interesting insights into the tuneability of the properties of this versatile class of π-conjugated macrocycles.
Issue Date: 23-Sep-2021
URI: http://hdl.handle.net/10044/1/99293
DOI: 10.12688/openreseurope.13723.1
ISSN: 2732-5121
Publisher: F1000Research
Copyright Statement: © 2021 Pletzer M et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Sponsor/Funder: FWF Austrian Science Fund (FWF)
Commission of the European Communities
EPRSC
Engineering & Physical Science Research Council (EPSRC)
Funder's Grant Number: J 4463
796024
EP/V048686/1
EP/V048686/1
Publication Status: Published
Open Access location: https://open-research-europe.ec.europa.eu/articles/1-111/v1
Appears in Collections:Chemistry



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