Supramolecular Self-Assembly of Perylene Bisimide-Based Rigid Giant Tetrahedra
- 28 July 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in ACS Nano
- Vol. 14 (7), 8266-8275
- https://doi.org/10.1021/acsnano.0c01971
Abstract
Recently, ordered structures constructed from rigid three-dimensional (3D) shaped polyhedra have been drawing general interest, with the tetrahedron being the simplest one but showing complicated assembly behaviors. Rigid tetrahedron building blocks have been shown to form quasicrystalline and crystalline phases with high packing fractions by both simulation and experiments. Nevertheless, the study of 3D tetrahedral building blocks is limited, especially in the field of supramolecular self-assembly. Here, we present an experimental study of rigid giant tetrahedral molecules constructed by attaching four bulky polyhedral oligomeric silsesquioxane (POSS) cages to a tetrahedral perylene bisimide (PBI) scaffold. Self-assembly of these giant tetrahedra is mediated by pi-pi interaction between the tetrahedral PBI-based scaffolds and their overall tetrahedral symmetry. A monolithic nearly centimeter-sized hexagonal supramolecular structure was observed in the giant tetrahedron with short flexible linkers between PBI and POSS cages, while a micrometer-sized crystalline helical structure formed in that with completely rigid aromatic linkers. Their significant difference in electrical conductivity could be explained by two completely different packing models of the giant tetrahedra.Funding Information
- Ministry of Education of the People's Republic of China (2019JQ05)
- National Natural Science Foundation of China (71890871, U1832220)
- Guangdong Province (2016ZT06C322, 2019B010941002, 2020B010182002)
- Key Laboratory of Functional and Intelligent Hybrid Materials and Devices (2019B121203003)
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