Covalently Interlocked Cyclohexa‐m‐phenylenes and Their Assembly: En Route to Supramolecular 3D Carbon Nanostructures

Abstract

In our search to cluster as many phenylene units as possible in a given space, we have proceeded to the three-dimensional world of benzene-based molecules by employing covalently interlocked cyclohexa-m-phenylenes, as present in the unique paddlewheel-shaped polyphenylene 10. A precursor was conceived, in which freely rotating m-chlorophenylene units provide sufficient solubility along with the necessary proximity for the final ring closure to give 10. Monitoring the assembly of solubilized tert-butyl derivatives of 10 into supramolecular carbon nanostructures by dynamic light scattering (DLS) and Brillouin light scattering (BLS) revealed the dimensions of the initially formed aggregates as well as the amorphous character of the solid state.

A Phenylene‐Bridged Cyclohexa‐meta‐phenylene as Hexa‐peri‐hexabenzocoronene Precursor

“…In summary, we demonstrated the synthesis and characterization of a cyclohexa‐ meta ‐phenylene 1 , as a unique 3D‐oligophenylene which also opens up a smooth access to hexa‐ peri ‐hexabenzocoronene in a surprisingly swift flattening process. We have shown in our previous work that interlocked cyclohexa‐ meta ‐phenylenes arrange in amorphous three‐dimensional carbon nanostructures with an extremely tight packing and have a quite high glass transition temperature . The title compound 1 , in contrast, is crystalline.…”

Over one century after discovery: pyrylium salt chemistry emerging as a powerful approach for the construction of complex macrocycles and metallo-supramolecules

“…In addition to phenylene bicyclophanes, the same strategy with rigid templates was used to construct 3D carbon nanostructures with increasing complexity, for instance, covalently interlocked cyclohexa-meta-phenylenes (25a-c in Figure 8). 125 Instead of the mechanical bond of catenanes, this paddlewheel-shaped molecule consists of two cyclohexa-metaphenylene rings which are orthogonal to each other but covalently interlocked. Within each cyclohexa-meta-phenylene, the central rigid template also serves as part of rigid hexaphenyl backbone.…”

Dual Ligand-Enabled Nondirected C–H Cyanation of Arenes

“…The assignment of 2f-meta and 2f-para was achieved by comparison with the literature. [7], [8] 1 H-NMR (CDCl3, 400 MHz): δ = 7.66 (s, 1H m ), 7.62 (d, J = 7.9 Hz, 1H m ), 7.58 (d, J = 8.4 Hz, 2H p ), 7.49-7.45 (m, 2H p +1H m ), 7.39 (t, J = 7.7 Hz, 1H m ), 1.33 (s, 9H) ppm. Following the general procedure B with 13% catalyst loading and using 2phenethylisoindoline-1,3-dione (50.3 mg, 0.200 mmol, 1 equiv) as the arene, the target compound 2g was obtained as a white solid (36.6 mg, 66%, o:m:p = 7:53:40).…”