Abstract
The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement. Here we show a chiral configuration of decapyrrylcorannulene that has a concave ‘palm’ of corannulene and ten flexible electron-rich pyrryl group ‘fingers’ to mimic the smart molecular ‘hands’ for self-adaptably cradling various buckyballs in a (+)hand-ball-hand(−) mode. As exemplified by crystallographic identification of 15 buckyball structures representing pristine, exohedral, endohedral, dimeric and hetero-derivatization, the pyrryl groups twist with varying dihedral angles to adjust the interaction between decapyrrylcorannulene and fullerene. The self-adaptable electron-rich pyrryl groups, susceptible to methylation, are theoretically revealed to contribute more than the bowl-shaped palm of the corannulene in holding buckyball structures. The generality of the present decapyrrylcorannulene host with flexible pyrryl groups facilitates the visualization of numerous unknown/unsolved fullerenes by crystallography and the assembly of the otherwise close-packed spherical fullerenes into two-dimensional layered structures by intercalation.
Highlights
The assembly of spherical fullerenes, or buckyballs, into single crystals for crystallographic identification often suffers from disordered arrangement
Crystallography is regarded as the most reliable approach towards the unambiguous identification of molecular structures, but the presence of severe disorder defects in the single crystals of spherical fullerenes frequently leads to ambiguous geometric identification
Inspired by the successful synthesis of corannulene polysulfide from decachlorocorannulene reported by Sigel et al.25. (Supplementary Note 1) and hexapyrrylbenzene from hexafluorobenzene reported by Henri[26], Meijer27and Muellen et al.[28], we conducted a reaction using pyrryl sodium with decachlorocorannulene 1 at 25 °C in DMF (Supplementary Notes 2-3)
Summary
Such an exceptional packing pattern might be mainly due to the influence of the flexible pyrryl groups, which afford multiple selfadaptable C-H∙∙∙π interactions (edge to face) in both the convexto-convex and concave-to-concave packing orientations. With the introduction of methyl groups, the previous convex-to-convex stacking orientation of 2a still exists in the packing structure of 2b, but the unique concaveto-concave stacking mode is transformed into a more compact cross-orthogonal packing pattern (see Supplementary Fig. 19 and Supplementary Data 1), with implication about 2b unsuitable for forming supramolecular assemblies with fullerenes in the crystal state. Average association constants (Ka) of 8252 and 5686 M−1 were determined for the a ba c
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