Nanographenic bowls based on contorted hexabenzocoronene: Synthesis, structure, and supramolecular assembly with
Yixun Sun1, Bo Yang1, Min Jia1
1School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
Abstract:
Buckybowls, the curved fragments of fullerenes, are attractive synthetic targets for exploring carbon nanomaterials, but constructing atomically well-defined, large multilayered architectures remains a formidable challenge. Here we report the synthesis of a class of coronene-bottomed nanographenic bowls, namely, tricarbon-annulated trifluorenocoronenes (TCTFCs), based on a contorted hexa-cata-hexabenzocoronene (c-HBC) skeleton. Two TCTFC derivatives bearing gem-diaryl or gem-dialkyl appendages were prepared via a "branching arms cyclization" (BAC) strategy. X-ray crystallography unambiguously confirms their C3-symmetric bowl-shaped geometry with bowl depths up to 2.3 angstrom and diameters exceeding 1 nanometer. These bowls exhibit red-shifted absorption/emission profiles, enhanced electron affinity, and reduced aromaticity relative to the c-HBC derivative. Notably, both compounds form 1:1 complexes with C60 in solution, while their cocrystals adopt columnar or honeycomb packing motifs. This work establishes a synthetic paradigm in constructing fully edge-closed c-HBC-based buckybowls, further delivering fundamental insights into their substituent-dependent host-guest binding and supramolecular assembly.
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