Surface-Confined Self-Assembled Janus Tectons: A Versatile Platform towards the Noncovalent Functionalization of Graphene

• Published in: Angewandte Chemie (International ed.) Vol. 53; no. 38; pp. 10060 - 10066
• Main Authors: Du, Ping, Jaouen, Maud, Bocheux, Amandine, Bourgogne, Cyril, Han, Zheng, Bouchiat, Vincent, Kreher, David, Mathevet, Fabrice, Fiorini-Debuisschert, Céline, Charra, Fabrice, Attias, André-Jean
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 15.09.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Edition: International ed. in English
• Subjects: Carbon; Chemistry; Chemistry, Multidisciplinary; Exposure; Flats; Graphene; Janus; Janus tectons; Physical Sciences; Physics; Platforms; scanning probe microscopy; Scanning tunneling microscopy; Science & Technology; Self assembly; Solids; Strategy; supramolecular chemistry; LIQUID-SOLID INTERFACE; ORGANIC-MOLECULES; ACID; REACTIVITY; RUTHENIUM ACETYLIDE COMPLEXES; NETWORKS; SINGLE-MOLECULE DYNAMICS; graphene; self-assembly; scanning probe microscopy; CYCLOPHANE; Janus tectons; METAL-SURFACES; supramolecular chemistry
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201403572

A general strategy for simultaneously generating surface‐based supramolecular architectures on flat sp2‐hybridized carbon supports and independently exposing on demand off‐plane functionality with controlled lateral order is highly desirable for the noncovalent functionalization of graphene. Here, we address this issue by providing a versatile molecular platform based on a library of new 3D Janus tectons that form surface‐confined supramolecular adlayers in which it is possible to simultaneously steer the 2D self‐assembly on flat C(sp2)‐based substrates and tailor the external interface above the substrate by exposure to a wide variety of small terminal chemical groups and functional moieties. This approach is validated throughout by scanning tunneling microscopy (STM) at the liquid–solid interface and molecular mechanics modeling studies. The successful self‐assembly on graphene, together with the possibility to transfer the graphene monolayer onto various substrates, should considerably extend the application of our functionalization strategy. Built to order: A library of Janus tectons equipped with small chemical groups or functional moieties has been synthesized. The self‐assembly on sp2‐hybridized carbon supports leads to the formation of well‐organized adlayers with the same lattice parameters, as demonstrated by STM. The external exposed surface presents a wide range of functionalities positioned with a precise lateral order.