Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks
Name
c9sc03348c.pdf
Description
Published version
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1.41 MB
Format
Adobe PDF
Checksum (MD5)
10a876e95ae05d282a7c80adc993bc67
Author(s)
Xie, Lilia S.
Alexandrov, Eugeny V.
Skorupskii, Grigorii
Proserpio, Davide M.
Dinca, Mircea
Date Issued
July 2019
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Xie, Lilia S. et al. "Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks." Chemical Science 37, 10 (July 2019): 8558-65 doi 10.1039/C9SC03348C ©2019 Author(s)
Version
Final published version
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution Noncommercial 3.0 unported license
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DOI of Published Version
https://doi.org/10.1039/C9SC03348C
