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

Lilia S. Xie, Eugeny V. Alexandrov, Grigorii Skorupskii, Davide M. Proserpio, Mircea Dincǎ

Research output: Contribution to journalArticlepeer-review

143 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)8558-8565
Number of pages8
JournalChemical Science
Volume10
Issue number37
DOIs
StatePublished - 2019
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry

Fingerprint

Dive into the research topics of 'Diverse π-π Stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal-organic frameworks'. Together they form a unique fingerprint.

Cite this