Supramolecular Tessellations by a Rigid Naphthalene Diimide Triangle

Tessellation of organic polygons though [pi center dot center dot center dot pi] and charge-transfer (CT) interactions offers a unique opportunity to construct supramolecular organic electronic materials with 2D topologies. Our approach to exploring the 3D topology of 2D tessellations of a naphthalene diimide-based molecular triangle (NDI-Delta) reveals that the 2D molecular arrangement is sensitive to the identity of the solvent and solute concentrations. Utilization of nonhalogenated solvents, combined with careful tailoring of the concentrations, results in NDI-Delta self-assembling though [pi center dot center dot center dot pi] interactions into 2D honeycomb triangular and hexagonal tiling patterns. Cocrystallization of NDI-Delta with tetrathiafulvalene (TTF) leads systematically to the formation of 2D tessellations as a result of superstructure-directing CT interactions. Different solvents lead to different packing arrangements. Using MeCN, CHCl3, and CH2Cl2, we identified three sets of cocrystals, namely CT-A, CT-B, and CT-C, respectively. Solvent modulation plays a critical role in controlling not only the NDI-Delta:TTF stoichiometric ratios and the molecular arrangements in the crystal superstructures, but also prevents the inclusion of TTF guests inside the cavities of NDI-Delta. Confinement of TTF inside the NDI-Delta 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 [Cl center dot center dot center dot Cl] and [Cl center dot center dot center dot S] intermolecular interactions, leading to the formation of a hexagonal grid of solvent in which NDI-Delta forms a triangular grid. In the CT-C superstructure, three TTF molecules self-assemble, forming a supramolecular isosceles triangle TTF-Delta, which tiles in a plane alongside the NDI-Delta, 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 center dot+ radical cations and one neutral TTF molecule.