Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks
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...
| Main Authors: | , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Royal Society of Chemistry (RSC)
2020
|
| Online Access: | https://hdl.handle.net/1721.1/126243 |
| _version_ | 1826201593130778624 |
|---|---|
| author | Xie, Lilia S. Alexandrov, Eugeny V. Skorupskii, Grigorii Proserpio, Davide M. Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Xie, Lilia S. Alexandrov, Eugeny V. Skorupskii, Grigorii Proserpio, Davide M. Dinca, Mircea |
| author_sort | Xie, Lilia S. |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T11:53:51Z |
| format | Article |
| id | mit-1721.1/126243 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T11:53:51Z |
| publishDate | 2020 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1262432022-10-01T06:49:13Z Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks Xie, Lilia S. Alexandrov, Eugeny V. Skorupskii, Grigorii Proserpio, Davide M. Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry 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. U.S. Department of Energy, Office of Basic Energy Sciences (Grant DE-SC0018235) National Science Foundation Graduate Research Fellowship Program (Grant 1122374) 2020-07-17T19:05:36Z 2020-07-17T19:05:36Z 2019-07 2019-06 2019-12-17T14:51:36Z Article http://purl.org/eprint/type/JournalArticle 2041-6539 https://hdl.handle.net/1721.1/126243 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) en 10.1039/C9SC03348C Chemical Science Creative Commons Attribution Noncommercial 3.0 unported license https://creativecommons.org/licenses/by-nc/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Xie, Lilia S. Alexandrov, Eugeny V. Skorupskii, Grigorii Proserpio, Davide M. Dinca, Mircea Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title | Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title_full | Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title_fullStr | Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title_full_unstemmed | Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title_short | Diverse π–π stacking motifs modulate electrical conductivity in tetrathiafulvalene-based metal–organic frameworks |
| title_sort | diverse π π stacking motifs modulate electrical conductivity in tetrathiafulvalene based metal organic frameworks |
| url | https://hdl.handle.net/1721.1/126243 |
| work_keys_str_mv | AT xielilias diverseppstackingmotifsmodulateelectricalconductivityintetrathiafulvalenebasedmetalorganicframeworks AT alexandroveugenyv diverseppstackingmotifsmodulateelectricalconductivityintetrathiafulvalenebasedmetalorganicframeworks AT skorupskiigrigorii diverseppstackingmotifsmodulateelectricalconductivityintetrathiafulvalenebasedmetalorganicframeworks AT proserpiodavidem diverseppstackingmotifsmodulateelectricalconductivityintetrathiafulvalenebasedmetalorganicframeworks AT dincamircea diverseppstackingmotifsmodulateelectricalconductivityintetrathiafulvalenebasedmetalorganicframeworks |