Abstract
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 language | English |
|---|---|
| Journal | Journal of the American Chemical Society |
| DOIs | |
| Publication status | Accepted/In press - Jan 1 2019 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Supramolecular tessellations by a rigid naphthalene diimide triangle. / Beldjoudi, Yassine; Narayanan, Ashwin; Roy, Indranil; Pearson, Tyler J.; Cetin, Muhammet Mustafa; Nguyen, Minh T.; Krzyaniak, Matthew D.; Alsubaie, Fehaid M.; Wasielewski, Michael R.; Stupp, Samuel I.; Stoddart, J. Fraser.
In: Journal of the American Chemical Society, 01.01.2019.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Supramolecular tessellations by a rigid naphthalene diimide triangle
AU - Beldjoudi, Yassine
AU - Narayanan, Ashwin
AU - Roy, Indranil
AU - Pearson, Tyler J.
AU - Cetin, Muhammet Mustafa
AU - Nguyen, Minh T.
AU - Krzyaniak, Matthew D.
AU - Alsubaie, Fehaid M.
AU - Wasielewski, Michael R.
AU - Stupp, Samuel I.
AU - Stoddart, J. Fraser
PY - 2019/1/1
Y1 - 2019/1/1
N2 - 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.
AB - 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.
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UR - http://www.scopus.com/inward/citedby.url?scp=85072986569&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b08758
DO - 10.1021/jacs.9b08758
M3 - Article
C2 - 31526001
AN - SCOPUS:85072986569
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
ER -