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 was synthesized via intramolecular Yamamoto coupling of an appropriate p-quinquephenyl derivative carrying four m-chlorophenyl substituents. The structural proof could be obtained by single-crystal X-ray diffraction analysis, which also revealed a slightly strained structure with an internal phenylene bridge. Notably, this cyclo-meta-phenylene served as a novel precursor for hexa-peri-hexabenzocoronene (HBC). The cyclodehydrogenation proceeded smoothly, providing the corresponding HBC derivative as confirmed by MALDI-TOF-MS, and UV/Vis spectroscopy.

Intramolecular methyl–methyl coupling on Au (111) is explored as a new on-surface protocol for edge extension in graphene nanoribbons (GNRs). Characterized by high-resolution scanning tunneling microscopy, noncontact atomic force microscopy, and Raman spectroscopy, the methyl–methyl coupling is proven to indeed proceed at the armchair edges of the GNRs, forming six-membered rings with sp3- or sp2-hybridized carbons.

Durch den Versuch, so viele Phenylen-Einheiten wie mçglich auf kleinstem Raum zu gruppieren, betreten wir die dreidimensionale Welt der benzolbasierten Moleküle.Indieser Arbeit ermçglichen wir dies durch das einzigartige,s chaufelradfçrmige Polyphenylen 10,w elches aus zwei kovalent gebundenen, ineinander verketteten Cyclohexa-m-phenylenen besteht. Es wurde ein Vorläufermolekülk onzipiert, welches frei rotierende m-Chlorphenylen-Einheiten trägt, die gleichermaßen eine ausreichende Lçslichkeit und die bençtigte räum-licheN ähe fürd ie finalen Ringschlüsse zu Struktur 10 ermçglichen. Die Selbstorganisation der lçslichen Derivate zu supramolekularen Kohlenstoffnanostrukturen wird nacheinander mittels dynamischer Lichtstreuung (DLS) und Brillouin-Lichtstreuung (BLS) untersucht, um die Dimensionen der im Anfangsstadium gebildeten Aggregate in Lçsung, sowie den amorphen Charakter im Festkçrper zu bestimmen.