An electrically conductive metallocycle: densely packed molecular hexagons with π-stacked radicals.

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, [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.

SUBMITTER: Cui M 

PROVIDER: S-EPMC9067574 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature