Abstract
The existence and the properties of a new 1D conjugated polymer, poly(sulfur acetylide), with –S–C\(\equiv \)C– repeating unit are predicted on the basis of density functional theory calculations. Depending on the conformation of the polymer, specifically on the C–S–C angles, the corresponding material is either a metallic conductor (C–S–C near linear) or a semiconductor (C–S–C not linear). It is a semiconductor with 1.6 eV band gap in the minimum energy conformation bent geometry. The polymer can be stretched out at a relatively large and impractical energy cost of 2.6 eV per –S–C\(\equiv \)C– unit upon which it becomes a metallic conductor. However, this semiconductor–metal transition appears to be unique in as much as it happens along a bending mode of the polymeric backbone. This new material appears to be easy to synthesize and is expected to be stable under normal conditions. Despite its simplicity and close relation to other well-known 1D conjugated polymers, such as poly(sulfur nitride) \(\hbox {(SN)}_{x}\), polyacetylene \(\hbox {(CH)}_{x}\) or polyyne (–C\(\equiv \)C–)\(_{x}\), poly(sulfur acetylide) still remains to be explored.
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Acknowledgments
The author of the present study gratefully acknowledges countless valuable discussions and an enduring support and mentorship to Professor Péter Surján, to whose 60th birthday this Festschrift is dedicated. Károly Németh started research on the field of theoretical design of small band gap conjugated polymers in 1990 as an undergraduate student in a collaborative research involving Professors Péter Surján and Jenő Kürti at Eötvös University, Budapest, Hungary [5]. This research has later been extended to various other topics of conjugated \(\pi \)-electron systems during the doctoral student period of the present author under the supervision of Professor Péter Surján, between 1992 and 1996 [51–54]. Recently, the present author’s research is centered around the theoretical design of functional materials for efficient electrochemical energy storage devices (batteries), especially those derived from conjugated \(\pi \)-electron systems, such as functionalized boron nitrides [55–57], still benefitting from the conjugated \(\pi \)-electron system studies conducted two decades ago with Professor Péter Surján. The author also thanks Prof. J. Kürti (Eötvös University, Budapest, Hungary) for helpful discussions in the subject of the present work and NERSC (U.S. DOE DE-AC02-05CH11231) for the use of computational resources.
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Published as part of the special collection of articles “Festschrift in honour of P. R. Surjan”.
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Németh, K. Metallic and semiconducting 1D conjugated polymers based on –S–C\(\equiv \)C– repeating units in poly(sulfur acetylide). Theor Chem Acc 134, 109 (2015). https://doi.org/10.1007/s00214-015-1704-9
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DOI: https://doi.org/10.1007/s00214-015-1704-9