<p>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.</p>

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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,
  • Xian-Sheng Ke

摘要

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.