Article,

Atomically precise single-crystal structures of electrically conducting 2D metal--organic frameworks

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Nature Materials, 20 (2): 222--228 (Feb 1, 2021)
DOI: 10.1038/s41563-020-00847-7

Abstract

Electrically conducting 2D metal--organic frameworks (MOFs) have attracted considerable interest, as their hexagonal 2D lattices mimic graphite and other 2D van der Waals stacked materials. However, understanding their intrinsic properties remains a challenge because their crystals are too small or of too poor quality for crystal structure determination. Here, we report atomically precise structures of a family of 2D $\pi$-conjugated MOFs derived from large single crystals of sizes up to 200þinspace$\mu$m, allowing atomic-resolution analysis by a battery of high-resolution diffraction techniques. A designed ligand core rebalances the in-plane and out-of-plane interactions that define anisotropic crystal growth. We report two crystal structure types exhibiting analogous 2D honeycomb-like sheets but distinct packing modes and pore contents. Single-crystal electrical transport measurements distinctively demonstrate anisotropic transport normal and parallel to the $\pi$-conjugated sheets, revealing a clear correlation between absolute conductivity and the nature of the metal cation and 2D sheet packing motif.

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