Synthesis of ordered carbonaceous frameworks from organic crystals

Hirotomo Nishihara, Tetsuya Hirota, Kenta Matsuura, Mao Ohwada, Norihisa Hoshino, Tomoyuki Akutagawa, Takeshi Higuchi, Hiroshi Jinnai, Yoshitaka Koseki, Hitoshi Kasai, Yoshiaki Matsuo, Jun Maruyama, Yuichiro Hayasaka, Hisashi Konaka, Yasuhiro Yamada, Shingi Yamaguchi, Kazuhide Kamiya, Takuya Kamimura, Hirofumi Nobukuni, Fumito Tani

Research output: Contribution to journalArticlepeer-review

53 Citations (Scopus)


Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.

Original languageEnglish
Article number109
JournalNature communications
Issue number1
Publication statusPublished - Dec 1 2017

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General
  • General Biochemistry,Genetics and Molecular Biology
  • General Physics and Astronomy


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