American Chemical Society, Journal of Physical Chemistry C, 39(120), p. 22627-22634, 2016
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We investigate here, by applying dispersion-corrected theoretical methods, the energy stability of dimers formed by [n]cycloparaphenylene molecules (n = 5, 6, 7, 8, 10, and 12 being the number of benzene rings strained to form the nanoring) when they self-assemble in crystalline samples. Their cyclic topology confers to these samples a rich variety of dimer orientations, i.e. tubular or herringbone-like, according to the nanoring size, with the final form of their crystal packing depending subtly on the energy difference and the number of symmetry-related repetitions between these two microstructures. We finally calculate the cohesive energies for the illustrative cases n = 6 and n = 12, through the interaction energies of the unique and symmetry-related supramolecular motifs found, to finally understand the driving forces between the emergence of nanochannel-like structures. ; This work is supported by the “Ministerio de Economía y Competitividad” of Spain and the “European Regional Development Fund” through Project CTQ2014-55073-P. M.M. thanks the E2TP-CYTEMA-SANTANDER program for financial support and the High Performance Computing Service of University Castilla-La Mancha for technical support.