Single crystal sapphire and diamond surfaces are used as planar, atomically flat insulating surfaces, for the deposition of the diacetylene compound 10,12-nonacosadiynoic acid. The surface assembly is compared with results on hexagonal boron nitride (h-BN), highly oriented pyrolytic graphite (HOPG) and MoS2 surfaces. A perfectly flat-lying monolayer of 10,12-nonacosadiynoic acid self-assembles on h-BN like on HOPG and MoS2. On sapphire and oxidized diamond surfaces, we observed assemblies of standing-up molecular layers. Surface assembly is driven by surface electrostatic dipoles. Surface polarity is partially controlled using a hydrogenated diamond surface or totally screened by the deposition of a graphene layer on the sapphire surface. This results in a perfectly flat and organized SAM on graphene, which is ready for on-surface polymerization of long and isolated molecular wires under ambient conditions.

International Center for Materials Nanoarchitectonics 1 1 Namiki Tsukuba Ibaraki 305 0044 Japan

International Center for Materials Nanoarchitectonics 1 1 Namiki Tsukuba Ibaraki 305 0044 Japan and Institute of Physics Czech Academy of Sciences Na Slovance 2 Prague 8 18221 Czech Republic

International Center for Materials Nanoarchitectonics 29 rue J Marvig 31055 Toulouse Cedex France

National Institute for Materials Science 1 1 Namiki Tsukuba Ibaraki 305 0044 Japan

National Institute for Materials Science Kyushu University Nishi ku Fukuoka 819 0395 Japan

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