Issue 5, 2022

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems

Abstract

Because supramolecular polymerization of emissive π-conjugated molecules depends strongly on π–π stacking interaction, the formation of well-defined one-dimensional nanostructures often results in a decrease or only a small increase of emission efficiency. This is also true for our barbiturate-based supramolecular polymers wherein hydrogen-bonded rosettes of barbiturates stack quasi-one-dimensionally through π–π stacking interaction. Herein we report supramolecular polymerization-induced emission of two regioisomeric 2,3-diphenylthiophene derivatives functionalized with barbituric acid and tri(dodecyloxy)benzyl wedge units. In CHCl3, both compounds are molecularly dissolved and accordingly poorly emissive due to a torsion-induced non-radiative decay. In methylcyclohexane-rich conditions, these barbiturates self-assemble to form crystalline nanofibers and exhibit strongly enhanced emission through supramolecular polymerization driven by hydrogen-bonding. Our structural analysis suggests that the barbiturates form a tape-like hydrogen-bonding motif, which is rationalized by considering that the twisted geometries of 2,3-diphenylthiophene cores prevend the competing rosettes from stacking into columnar supramolecular polymers. We also found that a small difference in the molecular polarity originating from the substitutional position of the thiophene core influences interchain association of the supramolecular polymers, affording different luminescent soft materials, gel and nanosheet.

Graphical abstract: Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems

Supplementary files

Article information

Article type
Edge Article
Submitted
10 11 2021
Accepted
08 12 2021
First published
09 12 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 1281-1287

Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems

M. Kawaura, T. Aizawa, S. Takahashi, H. Miyasaka, H. Sotome and S. Yagai, Chem. Sci., 2022, 13, 1281 DOI: 10.1039/D1SC06246H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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