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

Autor: Bliksted Roug Pedersen V; Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark., Price TW; Department of Chemistry and Biochemistry, Materials Science Institute, and, Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, OR 97403, USA., Kofod N; Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark., Zakharov LN; CAMCOR-Center for Advanced Materials Characterization in Oregon, University of Oregon, Eugene, Oregon, 97403, USA., Laursen BW; Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark., Jasti R; Department of Chemistry and Biochemistry, Materials Science Institute, and, Knight Campus for Accelerating Scientific Impact, University of Oregon, Eugene, OR 97403, USA., Brøndsted Nielsen M; Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 22; Vol. 30 (5), pp. e202303490. Date of Electronic Publication: 2023 Dec 05.
DOI: 10.1002/chem.202303490
Abstrakt: 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.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: