Polycyclic aromatic hydrocarbons (PAHs) show promise for applications in functional devices such as organic photovoltaics and field-effect transistors, but, although nanometre-sized PAHs—often referred to as nanographenes—have been well investigated as single-layer molecules, their multilayer counterparts remain rather unexplored. Here we show the assembly of a C64 nanographene derivative (comprising a planar core decorated with four meta-terphenyl–imide moieties at its periphery) into multilayer stacks with smaller PAHs ranging from naphthalene to ovalene and hexabenzocoronene. The functionalized C64 nanographene serves as a ditopic host that can accommodate a smaller PAH on either side of its planar core, in cavities delimited by its bulky imide substituents. Bilayers and trilayers (that is, complexes with 1:1 and 1:2 host:guest ratios, respectively) were observed in solution, and dimers of these complexes as well as multilayer compounds were isolated in the solid state. Quantum-chemical calculations indicate that dispersion forces are the main stabilizing factor for these complexes.
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Crystallographic data for the structures in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition nos. CCDC 2068629 (monolayer, 1), 2068630 (multilayer, [COR·1·COR]n), 2068631 (hexalayer, [COR·1·COR]2) and 2068632 (tetralayer, [COR·1·1·COR]). Copies of data can be obtained free of charge from www.ccdc.cam.ac.uk/structures/. Details of the synthesis and crystallographic analyses, UV–vis and fluorescence spectra, traces of cyclic and differential pulse voltammetry, plots of NMR titration and variable-temperature NMR experiments, DOSY NMR spectra, traces of ITC experiments and a description of the computational experiments are provided in the Supplementary Information. Source data are provided with this paper.
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We thank the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for financial support (grant no. WU 317/20-2).
The authors declare no competing interests.
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Details of synthesis, crystallographic analysis and computation. Supplementary Figs. 1–22 and Tables 1–15.
Crystal structure of monolayer 1; CCDC 2068629.
Crystal structure of polylayer _(COR-1-COR)n; CCDC 2068630.
Crystal structure of hexalayer (COR-1-COR)2; CCDC 2068631.
Crystal structure of tetralayer COR-1-1-COR; CCDC 2068632.
Source Data Supplementary Figs. 7, 11a–d, 12a–c, 13b–d, 14a–c and 15. Fit of proton-signals from a 1H NMR titration experiment. Fit of UV–vis titration experiments of nanographene 1 in chloroform solutions. Fit of fluorescence titration experiments of nanographene 1 in chloroform solutions. Comparison of the average Gibbs free energies from UV–vis and fluorescence titration experiments with different guest molecules.
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Mahl, M., Niyas, M.A., Shoyama, K. et al. Multilayer stacks of polycyclic aromatic hydrocarbons. Nat. Chem. 14, 457–462 (2022). https://doi.org/10.1038/s41557-021-00861-5