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Issue 37, 2019
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Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks

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Abstract

We report three electrically conductive metal–organic frameworks (MOFs) based on a tetrathiafulvalene linker and La3+. Depending on the solvent ratios and temperatures used in their solvothermal synthesis, these MOFs crystallize with different topologies containing distinct π–π stacking sequences of the ligand. Notably, their transport properties correlate rationally with the stacking motifs: longer S⋯S contact distances between adjacent ligands coincide with lower electrical conductivities and higher activation energies. Diffuse reflectance spectroscopic measurements reveal ligand-based intervalence charge transfer bands in each phase, implicating charge delocalization among mixed-valent tetrathiafulvalene units as the dominant mode of transport. Overall, these frameworks demonstrate how tuning the intermolecular interactions in MOFs serves as a route towards controlling their physical properties.

Graphical abstract: Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks

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Supplementary files

Article information


Submitted
06 Jul 2019
Accepted
31 Jul 2019
First published
01 Aug 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 8558-8565
Article type
Edge Article

Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks

L. S. Xie, E. V. Alexandrov, G. Skorupskii, D. M. Proserpio and M. Dincă, Chem. Sci., 2019, 10, 8558
DOI: 10.1039/C9SC03348C

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