Furan-Extended Helical Rylenes with Fjord Edge Topology and Tunable Optoelectronic Properties

Teng Luo; Yanpei Wang; Jiahang Hao; Ping-An Chen; Yuanyuan Hu; Bo Chen; Jun Zhang; Kun Yang; Zebing Zeng

doi:10.1002/anie.202214653

Furan-Extended Helical Rylenes with Fjord Edge Topology and Tunable Optoelectronic Properties

Angew Chem Int Ed Engl. 2023 Jan 26;62(5):e202214653. doi: 10.1002/anie.202214653. Epub 2022 Dec 22.

Authors

Teng Luo^{1

2}, Yanpei Wang^{1

2}, Jiahang Hao^{1

2}, Ping-An Chen³, Yuanyuan Hu³, Bo Chen⁴, Jun Zhang⁵, Kun Yang^{1

2}, Zebing Zeng^{1

2}

Affiliations

¹ Shenzhen Research Institute of Hunan University, Shenzhen, 518000, P. R. China.
² State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, P. R. China.
³ Key Laboratory for Micro/Nano Optoelectronic Devices of Ministry of Education, Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics and Devices School of Physics and Electronics, Hunan University, Changsha, 410082, P. R. China.
⁴ Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
⁵ School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei, 230039, P. R. China.

PMID: 36470852
DOI: 10.1002/anie.202214653

Abstract

Lateral furan-expansion of polycyclic aromatics, which enables multiple O-doping and peripheral edge evolution of rylenes, is developed for the first time. Tetrafuranylperylene TPF-4CN and octafuranylquaterrylene OFQ-8CN were prepared as model compounds bearing unique fjord edge topology and helical conformations. Compared to TPF-4CN, the higher congener OFQ-8CN displays a largely red-shifted (≈333 nm) and intensified absorption band (λ_max =829 nm) as well as a narrowed electrochemical band gap (≈1.08 eV) due to its pronounced π-delocalization and emerging of open-shell diradicaloid upon the increase of fjord edge length. Moreover, strong circular dichroism signals in a broad range until 900 nm are observed for open-shell chiral OFQ-8CN, owing to the excellent conformational stability of its central bis(tetraoxa[5]helicene) fragments. Our studies provide insights into the relationships between edge topologies and (chir)optoelectronic properties for this novel type of O-doped PAHs.

Keywords: Diradicaloids; Edge Topology; Open-Shell Structure; Oxygen-Doping; Rylene.

Abstract

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