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Polymers 2018, 10(2), 206; https://doi.org/10.3390/polym10020206

Self-Sensitization and Photo-Polymerization of Diacetylene Molecules Self-Assembled on a Hexagonal-Boron Nitride Nanosheet

1
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
2
Research Center for Functional Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
3
Centre d’Elaboration de Matériaux et d’Études Structurales (CEMES), Centre National de la Recherche Scientifique (CNRS), 29 rue J. Marvig, 31055 Toulouse CEDEX, France
*
Authors to whom correspondence should be addressed.
Received: 26 December 2017 / Revised: 1 February 2018 / Accepted: 17 February 2018 / Published: 19 February 2018
(This article belongs to the Special Issue Polymerizations from Surfaces)
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Abstract

Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light irradiation, with subsequent polymer identification by atomic force microscopy. The results on h-BN indicate self-sensitization which yields blocks comprised of several polymers, unlike on the well-studied graphite/diacetylene system, where the polymers are always isolated. In addition, the photo-polymerization proceeds at least 170 times faster on h-BN, where it also results in longer polymers. Both effects are explained by the h-BN bandgap, which is larger than the diacetylene electronic excitation energy, thus allowing the transfer of excess energy absorbed by polymerized wires to adjacent monomers, triggering their polymerization. This work sets the stage for conductance measurements of single molecular poly-diacetylene wires on h-BN. View Full-Text
Keywords: polymerization; diacetylene; self-assembly; h-BN surface; molecular wires; AFM; self-sensitization polymerization; diacetylene; self-assembly; h-BN surface; molecular wires; AFM; self-sensitization
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).
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Verveniotis, E.; Okawa, Y.; Watanabe, K.; Taniguchi, T.; Taniguchi, T.; Osada, M.; Joachim, C.; Aono, M. Self-Sensitization and Photo-Polymerization of Diacetylene Molecules Self-Assembled on a Hexagonal-Boron Nitride Nanosheet. Polymers 2018, 10, 206.

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