Synthesis and Properties of Fluorenone-Containing Cycloparaphenylenes and Their Late-Stage Transformation

Cycloparaphenylenes (CPPs) are the smallest possible armchair carbon nanotubes, the properties of which strongly depend on their ring size. They can be further tuned by either peripheral functionalization or by replacing phenylene rings for other aromatic units. Here we show how four novel donor-acceptor chromophores were obtained by incorporating fluorenone or 2-(9H-fluoren-9-ylidene)malononitrile into the loops of two differently sized CPPs. Synthetically, we managed to perform late-stage functionalization of the fluorenone-based rings by high-yielding Knoevenagel condensations. The structures were confirmed by X-ray crystallographic analyses, which revealed that replacing a phenylene for a fused-ring-system acceptor introduces additional strain. The donor-acceptor characters of the CPPs were supported by absorption and fluorescence spectroscopic studies, electrochemical studies (displaying the CPPs as multi-redox systems undergoing reversible or quasi-reversible redox events), as well as by computations. The oligophenylene parts were found to comprise the electron donor units of the macrocycles and the fluorenone parts the acceptor units. The synthesis and late-stage functionalization of donor-acceptor cycloparaphenylenes by incorporating fluorenone is presented, the process yields a selection of four nanohoops that vary in ring size and acceptor strength. Their donor-acceptor characters were supported by absorption and fluorescence spectroscopic studies as well as electrochemical and computational studies, and the geometries were elucidated by X-ray crystallography.image