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

Abstract

<jats:title>Abstract</jats:title><jats:p>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 (Ni<jats:sub>2</jats:sub>-CPD<jats:sub>Py</jats:sub>). This dimer comprises two Ni–porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni<jats:sub>2</jats:sub>-CPD<jats:sub>Py</jats:sub> 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–N<jats:sub>4</jats:sub> 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.</jats:p>

Topics

• impedance spectroscopy
• Carbon
• electrical conductivity
• Ni-containing