Precisely metal doped nanographenes via a carbaporphyrin approach

Haodan He, Jiyeon Lee, Zhaohui Zong, Ningchao Liu, Yoona Noh, Vincent M. Lynch, Juwon Oh (), Jiwon Kim (), Jonathan L. Sessler () and Xian-Sheng Ke ()
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Haodan He: Beijing Normal University
Jiyeon Lee: Yonsei University
Zhaohui Zong: Beijing Normal University
Ningchao Liu: Beijing Normal University
Yoona Noh: Soonchunhyang University
Vincent M. Lynch: The University of Texas at Austin
Juwon Oh: Soonchunhyang University
Jiwon Kim: Yonsei University
Jonathan L. Sessler: The University of Texas at Austin
Xian-Sheng Ke: Beijing Normal University

Nature Communications, 2025, vol. 16, issue 1, 1-10

Abstract: Abstract Nanographenes, finite models of graphene sheets, are endowed with intriguing optical, electronic, and spintronic features. So-called heteroatom-doping, where one or more carbon is replaced by non-carbon light atoms has been proved effective in tuning the properties of nanographenes. Here we extend the concept of heteroatom nanographene doping to include metal centers. The method employed involves the use of a dipyrromethene fragment as an auxiliary ligand that is directly linked to the bay area of the model nanographene hexa-peri-hexabenzocoronene (HBC) to give a dipyrromethene-fused nanographene-type hybrid ligand (HBCP). HBCP has a corrole-like trianionic core that is capable of coordinating group 11 metal cations, including trivalent Cu, Ag and Au. These cations are introduced into the cavity with atomic precision to give metal complexes (HBCP-M; M = Cu, Ag, Au). The electronic structure and photophysical properties of HBCP and its metal complexes are investigated by steady-state and fs-transient spectroscopies, as well as DFT calculations. The ligand and metal complexes are also characterized via single crystal X-ray diffraction analyses. This work paves the way towards the precise metal doping of nanographenes within the carbon network, as opposed to the synthetic appendage of an independent chelating group, such as a fused tetrapyrrolic moiety.

Date: 2025
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DOI: 10.1038/s41467-025-56828-4

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