Supramolecular architectures of molecularly thin yet robust free-standing layers

In a collaboration within the network of the Swiss Nanoscience Institute, the formation of free-standing molecular monolayers using self-assembly processes has been demonstrated. The results of the study have been published in the February 2019 issue of Science Advances.

Cryo-TEM investigation of a free-standing monolayer of a calixarene derivative. The TEM-Picture on the left shows the monolayer deposited on a lacey carbon support. The electron diffraction pattern on the left confirms the formation of a crystalline monolayer

Stable, single-nanometer thin, and free-standing two-dimensional layers with controlled molecular architectures are desired for 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 demonstrate that relatively weak noncovalent bonds of limited directionality such as dipole-dipole (–CN⋅⋅⋅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.

Original Publication
M. Moradi, N. L. Opara, L. G. Tulli, C. Wäckerlin, S. J. Dalgarno, S. J. Teat, M. Baljozovic, O. Popova, E. van Genderen, A. Kleibert, H. Stahlberg, J. P. Abrahams, C. Padeste, P. F.-X. Corvini, T. A. Jung, P. Shahgaldian, Supramolecular architectures of molecularly thin yet robust freestanding layers. Sci. Adv. 5, eaav4489 (2019). DOI: 10.1126/sciadv.aav4489