Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

作者：Martin Pfeffermann, Renhao Dong⧫, Robert Graf, Wojciech Zajączkowski, Tatiana E. Gorelik, Wojciech Pisula, Akimitsu Narita, Kläus Müllen, Xinliang Feng · 发表于：Journal of the American Chemical Society · 年份：2015 · DOI：10.1021/jacs.5b09638 · 被引用次数：202 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Supramolecular Chemistry and Complexes、Supramolecular Self-Assembly in Materials

Utilizing dynamic self-assembly and self-sorting to obtain large-area, molecularly precise monolayered structures represents a promising approach toward two-dimensional supramolecular organic frameworks (2D SOF) or 2D supramolecular polymers. So far, related approaches suffer from small domain sizes, fragility and weak long-range internal order. Here we report on the self-assembly of a host-guest enhanced donor-acceptor interaction, consisting of a tris(methoxynaphthyl)-substituted truxene spacer, and a naphthalene diimide substituted with N-methyl viologenyl moieties as donor and acceptor monomers, respectively, in combination with cucurbit[8]uril as host monomer toward monolayers of an unprecedented 2D SOF. Featuring orthogonal solubility, the participating molecules self-assemble at a liquid-liquid interface, yielding exceptionally large-area, insoluble films, which were analyzed by transmission electron microscopy, atomic force microscopy and optical microscopy to be monolayers with a thickness of 1.8 nm, homogeneously covering areas up to 0.25 cm(2), and featuring the ability to be free-standing over holes of 10 μm(2). Characterization with ultraviolet-visible absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, infrared spectroscopy, and grazing incidence wide-angle X-ray scattering allowed for confirmation of a successful complexation of all three monomers toward an internal long-range order and gave indications to an expected hexagonal superst...