Sakurai Takahiro, Tanabe Tappei, Iguchi Hiroaki, Li Zhuowei, Matsuda Wakana, Tsutsui Yusuke, Seki Shu, Matsuda Ryotaro, Shinokubo Hiroshi
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University Furo-cho, Chikusa-ku Nagoya 464-8603 Japan
Department of Material Chemistry, Graduate School of Engineering, Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University Furo-cho, Chikusa-ku Nagoya 464-8603 Japan
Chem Sci. 2024 Jul 11;15(32):12922-12927. doi: 10.1039/d4sc03455d. eCollection 2024 Aug 14.
Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and -nitrogen atoms. The thermal and chemical stabilities of the HOF were examined using powder X-ray diffraction analysis, and the charge-carrier mobility was determined to be 2.0 × 10 m V s using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method. An analogous diazaporphyrin, which does not form a HOF, exhibited mobility that was 20 times lower. The results presented herein highlight the crucial role of hydrogen-bonding networks in achieving conductive pathways that can tolerate thermal perturbation.
人们已经付出了巨大努力来开发兼具高电导率和永久孔隙率的材料。本文披露了一种基于二氮杂卟啉的氢键有机框架（HOF），它具有孔隙率和n型半导体特性。一种在β位带有羧基苯基的5,15 - 二氮杂卟啉镍（II）配合物，由于羧基与β - 氮原子之间的氢键相互作用而形成了一种HOF。使用粉末X射线衍射分析研究了该HOF的热稳定性和化学稳定性，并通过闪光光解时间分辨微波电导率（FP - TRMC）方法确定其电荷载流子迁移率为2.0×10⁻³ m² V⁻¹ s⁻¹。一种类似的不能形成HOF的二氮杂卟啉，其迁移率比该HOF低20倍。本文给出的结果突出了氢键网络在实现能够耐受热扰动的导电通道方面的关键作用。
