TY - JOUR
T1 - An electrically conductive metallocycle
T2 - densely packed molecular hexagons with π-stacked radicals
AU - Cui, Mengxing
AU - Murase, Ryuichi
AU - Shen, Yongbing
AU - Sato, Tetsu
AU - Koyama, Shohei
AU - Uchida, Kaiji
AU - Tanabe, Tappei
AU - Takaishi, Shinya
AU - Yamashita, Masahiro
AU - Iguchi, Hiroaki
N1 - Funding Information:
We acknowledge the support from Prof Akutagawa and Dr Hoshino at Tohoku University for acquiring the ESR spectra. We also thank Prof Iwamoto and Dr Ishida at Tohoku University for the preliminary SXRD analysis. This work was partly supported by JSPS KAKENHI Grant Numbers JP18H04498 (H. I.), JP19H05631 (H. I., S. T. and M. Y.), JP21H01901 (H. I.) and JP21K18971 (H. I.), by the Toyota Riken Scholar Program (H. I.), by the Kato Foundation for Promotion of Science KJ-2916 (H. I.), and by the Iketani Science and Technology Foundation 0331101-A (H. I.). M. Y. acknowledges the support from the 111 project (B18030) from China. M. C. gratefully acknowledges the financial support from the Chinese Scholarship Council (CSC).
Publisher Copyright:
© 2022 The Royal Society of Chemistry
PY - 2022/4/1
Y1 - 2022/4/1
N2 - 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, [Ni6(NDI-Hpz)6(dma)12(NO3)6]·5DMA·nH2O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-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 H2O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2-2.1) × 10−4 S cm−1 (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.
AB - 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, [Ni6(NDI-Hpz)6(dma)12(NO3)6]·5DMA·nH2O (PMC-hexagon) (NDI-Hpz = N,N′-di(1H-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 H2O molecules. The NDI cores were partially reduced to form radicals as charge carriers, resulting in a room-temperature conductivity of (1.2-2.1) × 10−4 S cm−1 (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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U2 - 10.1039/d2sc00447j
DO - 10.1039/d2sc00447j
M3 - Article
AN - SCOPUS:85129503311
SN - 2041-6520
VL - 13
SP - 4902
EP - 4908
JO - Chemical Science
JF - Chemical Science
IS - 17
ER -