An Electrically Conductive Metallocycle: Densely Packed Molecular Hexagons with π-stacked Radicals

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Jun 3

PMID 35655871

Authors

Mengxing Cui

Ryuichi Murase

Yongbing Shen

Tetsu Sato

Shohei Koyama

Kaiji Uchida

Tappei Tanabe

Shinya Takaishi

Masahiro Yamashita

Hiroaki Iguchi

Affiliations

Soon will be listed here.

Abstract

Electrical conduction among metallocycles has been unexplored because of the difficulty in creating electronic transport pathways. In this work, we present an electrocrystallization strategy for synthesizing an intrinsically electron-conductive metallocycle, [Ni(NDI-Hpz)(dma)(NO)]·5DMA·HO (PMC-hexagon) (NDI-Hpz = ,'-di(1-pyrazol-4-yl)-1,4,5,8-naphthalenetetracarboxdiimide). The hexagonal metallocycle units are assembled into a densely packed ABCABC… sequence (like the fcc geometry) to construct one-dimensional (1D) helical π-stacked columns and 1D pore channels, which were maintained under the liberation of HO molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2-2.1) × 10 S cm (pressed pellet), which is superior to that of most NDI-based conductors including metal-organic frameworks and organic crystals. These findings open up the use of metallocycles as building blocks for fabricating conductive porous molecular materials.

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