Rigid three-dimensional (3D) polycyclic aromatic hydrocarbons (PAHs), in particular 3D nanographenes, have garnered interest due to their potential use in semiconductor applications and as models to study through-bond and through-space electronic interactions. Herein we report the development of a novel 3D-symmetric rylene imide building block, triperyleno[3,3,3]propellane triimides (6), that possesses three perylene monoimide subunits fused on a propellane. This building block shows several promising characteristics, including high solubility, large π-surfaces, electron-accepting capabilities, and a variety of reactive sites. Further, the building block is compatible with different reactions to readily yield quasi-D3h symmetric nanostructures (9, 11, and 13) of varied chemistries. For the 3D nanostructures we observed red-shift absorption maxima and amplification of the absorption coefficients when compared to the individual subunits, indicating intramolecular electronic coupling among the subunits. In addition, the microplates of 9 exhibit comparable mobilities in different directions in the range of 10−3 cm2 V−1 s−1, despite the rather limited intermolecular overlap of the π-conjugated moieties. These findings demonstrate that these quasi-D3h symmetric rylene imides have potential as 3D nanostructures for a range of materials applications, including in organic electronic devices.
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L. Z. thanks the National Science Foundation of China (NSFC) (21672020 and 21871022) and the Beijing Natural Science Foundation (2182049). L. L. thanks the Distinguished Scientist Program at BUCT (buctylkxj02). C. X. thanks the China Postdoctoral Science Foundation (2017M610744). C. R. acknowledges funding from the National Science Foundation Designing Materials to Revolutionize and Engineer our Future (NSF DMREF) program under Award DMR-1627428.
Electronic supplementary information (ESI) available: Detailed synthesis and characterization of the compounds; 1H NMR, 13C NMR, HMBC, and 1D NOE spectra of the compounds; crystal data for 9; UV spectra and CV curves; theoretical calculation details; device fabrication and characterization. CCDC 1894754. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9sc00849g
Lv, Lingling; Roberts, Josiah; Xiao, Chengyi; Jia, Zhenmei; Jiang, Wei; Risko, Chad; and Zhang, Lei, "Triperyleno[3,3,3]propellane Triimides: Achieving a New Generation of Quasi-D3h Symmetric Nanostructures in Organic Electronics" (2019). Chemistry Faculty Publications. 162.