10.1021/jacs.9b08758.s005
Yassine Beldjoudi
Yassine
Beldjoudi
Ashwin Narayanan
Ashwin
Narayanan
Indranil Roy
Indranil
Roy
Tyler J. Pearson
Tyler J.
Pearson
M. Mustafa Cetin
M. Mustafa
Cetin
Minh T. Nguyen
Minh T.
Nguyen
Matthew D. Krzyaniak
Matthew D.
Krzyaniak
Fehaid M. Alsubaie
Fehaid M.
Alsubaie
Michael R. Wasielewski
Michael R.
Wasielewski
Samuel I. Stupp
Samuel I.
Stupp
J. Fraser Stoddart
J. Fraser
Stoddart
Supramolecular
Tessellations by a Rigid Naphthalene
Diimide Triangle
American Chemical Society
2019
CHCl 3 lattice molecules
absorption band
NDI -Δ
NIR
3 honeycomb tiling pattern
NDI -Δ forms
CT-B
CT-C
CT-A
NDI -Δ self-assembling
Solid-state spectroscopic investigations
3 D topology
2 D honeycomb
supramolecular isosceles triangle TTF -Δ
superstructure-directing CT interactions
NDI -Δ cavities
2 D tessellations
CH 2 Cl 2
TTF stoichiometric ratios
Rigid Naphthalene Diimide Triangle Tessellation
TTF molecules self-assemble
2 D topologies
TDDFT
2019-10-22 13:39:56
Dataset
https://acs.figshare.com/articles/dataset/Supramolecular_Tessellations_by_a_Rigid_Naphthalene_Diimide_Triangle/10012628
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 to exploring the 3D topology of 2D tessellations of a
naphthalene diimide-based molecular triangle (<b>NDI-Δ</b>) 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 <b>NDI-Δ</b> self-assembling though [π···π]
interactions into 2D honeycomb triangular and hexagonal tiling patterns.
Cocrystallization of <b>NDI-Δ</b> with tetrathiafulvalene
(<b>TTF</b>) 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, CHCl<sub>3</sub>, and CH<sub>2</sub>Cl<sub>2</sub>, we identified three sets
of cocrystals, namely <b>CT-A</b>, <b>CT-B</b>, and <b>CT-C</b>, respectively. Solvent modulation plays a critical role
in controlling not only the <b>NDI-Δ</b>:<b>TTF</b> stoichiometric ratios and the molecular arrangements in the crystal
superstructures, but also prevents the inclusion of <b>TTF</b> guests inside the cavities of <b>NDI-Δ</b>. Confinement
of <b>TTF</b> inside the <b>NDI-Δ</b> cavities in
the <b>CT-A</b> superstructure enhances the CT character with
the observation of a broad absorption band in the NIR region. In the <b>CT-B</b> superstructure, the CHCl<sub>3</sub> lattice molecules
establish a set of [Cl···Cl] and [Cl···S]
intermolecular interactions, leading to the formation of a hexagonal
grid of solvent in which <b>NDI-Δ</b> forms a triangular
grid. In the <b>CT-C</b> superstructure, three <b>TTF</b> molecules self-assemble, forming a supramolecular isosceles triangle <b>TTF-Δ</b>, which tiles in a plane alongside the <b>NDI-Δ</b>, producing a 3 + 3 honeycomb tiling pattern of the two different
polygons. Solid-state spectroscopic investigations on <b>CT-C</b> 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 <b>TTF</b><sup><b>•+</b></sup> radical cations and one neutral <b>TTF</b> molecule.