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Issue 8, 2013
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Synthesis and electronic structure of a two dimensional π-conjugated polythiophene

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Abstract

We report the synthesis and first electronic characterization of an atomically thin two dimensional π-conjugated polymer. Polymerization via Ullmann coupling of a tetrabrominated tetrathienoanthracene on Ag(111) in ultra-high vacuum (UHV) produces a porous 2D polymer network that has been characterized by scanning tunnelling microscopy (STM). High-resolution X-ray photoelectron spectroscopy (HRXPS) shows that the reaction proceeds via two distinct steps: dehalogenation of the brominated precursor, which begins at room temperature (RT), and C–C coupling of the resulting Ag-bound intermediates, which requires annealing at 300 °C. The formation of the 2D conjugated network is accompanied by a shift of the occupied molecular states by 0.6 eV towards the Fermi level, as observed by UV photoelectron spectroscopy (UPS). A theoretical analysis of the electronic gap reduction in the transition from monomeric building blocks to various 1D and 2D oligomers and polymers yields important insight into the effect of topology on the electronic structure of 2D conjugated polymers.

Graphical abstract: Synthesis and electronic structure of a two dimensional π-conjugated polythiophene

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Article information


Submitted
24 Mar 2013
Accepted
19 May 2013
First published
21 May 2013

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2013,4, 3263-3268
Article type
Edge Article

Synthesis and electronic structure of a two dimensional π-conjugated polythiophene

L. Cardenas, R. Gutzler, J. Lipton-Duffin, C. Fu, J. L. Brusso, L. E. Dinca, M. Vondráček, Y. Fagot-Revurat, D. Malterre, F. Rosei and D. F. Perepichka, Chem. Sci., 2013, 4, 3263
DOI: 10.1039/C3SC50800E

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