72.
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
6(NDI-Hpz)
6(dma)
12(NO
3)
6]·5DMA·
nH
2O (PMC-hexagon) (NDI-Hpz =
N,
N′-di(1
H-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 H
2O 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.Intrinsically electron-conductive metallocycle was synthesized. π-Radicals play a key role in constructing π-stacked columns among molecular hexagons and achieving high electrical conductivity over 10
−4 S cm
−1 in polycrystalline pellet.
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