Toward a Single-Layer Two-Dimensional Honeycomb Supramolecular Organic Framework in Water

Kang-Da Zhang, Jia Tian, David Hanifi, Yuebiao Zhang, Andrew Chi-Hau Sue, Tian-You Zhou, Lei Zhang,
Xin Zhao*, Yi Liu*, and Zhan-Ting Li*
J. Am. Chem. Soc. 2013, 135, 17913–17918 (Highlighted as Front Cover)
The self-assembly of well-defined 2D supramolecular polymers in solution has been a challenge in supramolecular chemistry. We have designed and synthesized a rigid stacking-forbidden 1,3,5-triphenylbenzene compound that bears three 4,4′-bipyridin-1-ium (BP) units on the peripheral benzene rings. Three hydrophilic bis(2-hydroxyethyl)carbamoyl groups are introduced to the central benzene ring to suppress 1D stacking of the triangular backbone and to ensure solubility in water. Mixing the triangular preorganized molecule with cucurbit[8]uril (CB[8]) in a 2:3 molar ratio in water leads to the formation of the first solution-phase single-layer 2D supramolecular organic framework, which is stabilized by the strong complexation of CB[8] with two BP units of adjacent molecules. The periodic honeycomb 2D framework has been characterized by various 1H NMR spectroscopy, dynamic light scattering, X-ray diffraction and scattering, scanning probe and electron microscope techniques and by comparing with the self-assembled structures of the control systems.