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    Supramolecular architectures of molecularly thin yet robust free-standing layers

    Year: 2019

    Journal: Sci. Adv., Volume 5, FEB

    Authors: Moradi, Mina; Opara, Nadia L.; Tulli, Ludovico G.; Waeckerlin, Christian; Dalgarno, Scott J.; Teat, Simon J.; Baljozovic, Milos; Popova, Olha; van Genderen, Eric; Kleibert, Armin; Stahlberg, Henning; Abrahams, Jan Pieter; Padeste, Celestino; Corvini, Philippe F-X; Jung, Thomas A.; Shahgaldian, Patrick

    Organizations: Swiss Nanoscience Institute [P1305, P1308]; University Research Priority Program LightChEC of the University of Zurich, Switzerland; Swiss National Science FoundationSwiss National Science Foundation (SNSF) [200020-153549, 200020-175800, 206021-113149]; DOE Office of Science User FacilityUnited States Department of Energy (DOE) [DE-AC02-05CH11231]; SNF [5204.23000.160.02]

    Stable, single-nanometer thin, and free-standing two-dimensional layers with controlled molecular architectures are desired for several applications ranging from (opto-)electronic devices to nanoparticle and single-biomolecule characterization. It is, however, challenging to construct these stable single molecular layers via self-assembly, as the cohesion of those systems is ensured only by in-plane bonds. We herein demonstrate that relatively weak noncovalent bonds of limited directionality such as dipole-dipole (-CN center dot center dot center dot NC-) interactions act in a synergistic fashion to stabilize crystalline monomolecular layers of tetrafunctional calixarenes. The monolayers produced, demonstrated to be freestanding, display a well-defined atomic structure on the single-nanometer scale and are robust under a wide range of conditions including photon and electron radiation. This work opens up new avenues for the fabrication of robust, single-component, and free-standing layers via bottom-up self-assembly.
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