Supramolecular tessellations by a rigid naphthalene diimide triangle

Yassine Beldjoudi, Ashwin Narayanan, Indranil Roy, Tyler J. Pearson, Muhammet Mustafa Cetin, Minh T. Nguyen, Matthew D. Krzyaniak, Fehaid M. Alsubaie, Michael R. Wasielewski, Samuel I. Stupp, J. Fraser Stoddart

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Tessellation of organic polygons though [π⋯π] and charge-transfer (CT) interactions offers a unique opportunity to construct supramolecular organic electronic materials with 2D topologies. Our approach of exploring the 3D topology of 2D tessellations of a naphthalene diimide-based molecular triangle (NDI-δ) reveals that the 2D molecular arrangement is sensitive to the identity of the solvent and solute concentrations. Utilization of non-halogenated solvents, combined with careful tailoring of the concentrations, results in NDI-δ self-assembling though [π⋯π] interactions into 2D honeycomb triangular and hexagonal tiling patterns. Co-crystallization of NDI-δ with tetrathiafulvalene (TTF) leads systematically to the formation of 2D tessellations as a result of superstructure directing of CT interactions. Different solvents lead to different packing arrangements. Using MeCN, CHCl3 and CH2Cl2, we identified three sets of co-crystals, namely CT-A, CT-B, and CT-C respectively. Solvent modulation plays a critical role in controlling, not only the NDI-δ:TTF stoichiometric ratios and the molecular arrangements in the crystal superstructures, but also prevents the inclusion of TTF guests inside the cavities of NDI-δ. Confinement of TTF inside the NDI-δ cavities in the CT-A superstructure enhances the CT character with the observation of a broad absorption band in the NIR region. In the CT-B superstructure, the CHCl3 lattice molecules establish a set of [ClCl] and [ClS] intermolecular interactions, leading to the formation of a hexagonal grid of solvent in which NDI-Δforms a triangular grid. In the CT-C superstructure, three TTF molecules self-assemble, forming a supramolecular isosceles, triangle TTF-δ, which tiles in a plane alongside the NDI-δ producing a 3+3 honeycomb tiling pattern of the two different polygons. Solid-state spectroscopic investigations on CT-C, revealed the existence of an absorption band at 2500 nm which, on the basis of TDDFT calculations was attributed to the mixed-valence character between two TTF•+ and one neutral TTF molecule.

Original languageEnglish
JournalJournal of the American Chemical Society
Publication statusAccepted/In press - Jan 1 2019


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Beldjoudi, Y., Narayanan, A., Roy, I., Pearson, T. J., Cetin, M. M., Nguyen, M. T., Krzyaniak, M. D., Alsubaie, F. M., Wasielewski, M. R., Stupp, S. I., & Stoddart, J. F. (Accepted/In press). Supramolecular tessellations by a rigid naphthalene diimide triangle. Journal of the American Chemical Society.