Rh‐Catalyzed [2 + 2 + 2] Cycloaddition of Linked Bis(Diynes) Ar‐C≡C‐C≡C‐(CH <sub>2</sub> ) <sub>3</sub> ‐C≡C‐C≡C‐Ar With Quinones: Synthesis and Photophysical Properties of Bis(Arylethynyl)‐Naphthoquinones and Anthraquinones
Herein, we report the Rh-catalyzed [2 + 2 + 2] cycloaddition of linked bis(diynes) Ar-C≡C-C≡C-(CH<sub>2</sub>)<sub>3</sub>-C≡C-C≡C-Ar with quinones for the rapid and efficient assembly of rigid structures containing bis(arylethynyl)naphthoquinones or anthraquinones using microwave radiation. The photophysical properties of the products were investigated, including absorption, emission, transient absorption (TA) spectroscopy, and singlet oxygen luminescence studies. However, the quinones did not exhibit photoluminescence or detectable singlet oxygen luminescence. Computational analysis via density functional theory (DFT) was performed to elucidate the electronic and structural factors influencing their behavior. Moreover, reductive methylation of one of the bis(arylethynyl)naphthoquinones (3aa) generated the fluorescent bis(methoxy) naphthalene derivative 4aa (Φ<sub>f</sub> = 0.53). However, 4aa underwent photooxidation in air under sunlight via reaction with <sup>1</sup>O<sub>2</sub>, which it sensitized, leading to ring opening of the bis(methoxy)arene ring.
Authors
- Todd B. Marder (ORCID: https://orcid.org/0000-0002-9990-0169)
- Jean‐François Halet
- Camille Latouche (ORCID: https://orcid.org/0000-0002-3541-3417)
- Qing Ye (ORCID: https://orcid.org/0000-0002-7238-0407)
- Fábio G. Delolo (ORCID: https://orcid.org/0000-0001-7968-9506)
- Christoph Lambert (ORCID: https://orcid.org/0000-0002-9652-9165)
- Leibo Tan
- Eufrânio N. da Silva Júnior
- Breno U. Abreu
- Tobias Groß
- Joyce C. Oliveira
- Joannes Krebs
- Holger Braunschweig
- Jianhua Han
- Hállen D. R. Calado
- Luana A. Machado
Institutions
- Universidade Federal de Minas Gerais (BR)
- Centre National de la Recherche Scientifique (FR)
- Institut Universitaire de France (FR)
- University of Würzburg (DE)
- Institut des Matériaux Jean Rouxel (FR)
- École Nationale Supérieure de Chimie de Rennes (FR)
- Bavarian Polymer Institute (DE)
- Université de Rennes (FR)
Publication Details
- Journal
- Chemistry - A European Journal
- Published
- 2026-01-14
- DOI
- https://doi.org/10.1002/chem.202503173
- Primary Topic
- Synthesis and Properties of Aromatic Compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Deutscher Akademischer Austauschdienst
- Deutsche Forschungsgemeinschaft
- Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
- Conselho Nacional de Desenvolvimento Científico e Tecnológico
- Fundação de Amparo à Pesquisa do Estado de Minas Gerais
- Julius-Maximilians-Universität Würzburg