Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks
Isostructural metal–organic frameworks (MOFs) M[subscript 2](TTFTB) (M = Mn, Co, Zn, and Cd; H[subscript 4]TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which i...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2017
|
| Online Access: | http://hdl.handle.net/1721.1/110489 https://orcid.org/0000-0002-7837-8412 https://orcid.org/0000-0002-6547-3402 https://orcid.org/0000-0001-7111-0176 https://orcid.org/0000-0002-1262-1264 |
| _version_ | 1811092655561506816 |
|---|---|
| author | Hendon, Christopher H. Walsh, Aron Park, Sarah Sunah Hontz, Eric Richard Sun, Lei Van Voorhis, Troy Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Hendon, Christopher H. Walsh, Aron Park, Sarah Sunah Hontz, Eric Richard Sun, Lei Van Voorhis, Troy Dinca, Mircea |
| author_sort | Hendon, Christopher H. |
| collection | MIT |
| description | Isostructural metal–organic frameworks (MOFs) M[subscript 2](TTFTB) (M = Mn, Co, Zn, and Cd; H[subscript 4]TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10[subscript –4] S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs. |
| first_indexed | 2024-09-23T15:21:32Z |
| format | Article |
| id | mit-1721.1/110489 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:21:32Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1104892022-09-29T14:29:54Z Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks Hendon, Christopher H. Walsh, Aron Park, Sarah Sunah Hontz, Eric Richard Sun, Lei Van Voorhis, Troy Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Park, Sarah Sunah Hontz, Eric Richard Sun, Lei Van Voorhis, Troy Dinca, Mircea Isostructural metal–organic frameworks (MOFs) M[subscript 2](TTFTB) (M = Mn, Co, Zn, and Cd; H[subscript 4]TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10[subscript –4] S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs. United States. Department of Energy. Office of Basic Energy Sciences (Award DE-SC0006937) National Science Foundation (U.S.). Graduate Research Fellowship Program (Award 1122374) David & Lucile Packard Foundation (Fellowship) 2017-07-06T15:22:49Z 2017-07-06T15:22:49Z 2015-01 2014-12 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/110489 Park, Sarah S. et al. “Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks.” Journal of the American Chemical Society 137.5 (2015): 1774–1777. © 2015 American Chemical Society https://orcid.org/0000-0002-7837-8412 https://orcid.org/0000-0002-6547-3402 https://orcid.org/0000-0001-7111-0176 https://orcid.org/0000-0002-1262-1264 en_US http://dx.doi.org/10.1021/ja512437u Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Hendon, Christopher H. Walsh, Aron Park, Sarah Sunah Hontz, Eric Richard Sun, Lei Van Voorhis, Troy Dinca, Mircea Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title | Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title_full | Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title_fullStr | Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title_full_unstemmed | Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title_short | Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks |
| title_sort | cation dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene based microporous metal organic frameworks |
| url | http://hdl.handle.net/1721.1/110489 https://orcid.org/0000-0002-7837-8412 https://orcid.org/0000-0002-6547-3402 https://orcid.org/0000-0001-7111-0176 https://orcid.org/0000-0002-1262-1264 |
| work_keys_str_mv | AT hendonchristopherh cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT walsharon cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT parksarahsunah cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT hontzericrichard cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT sunlei cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT vanvoorhistroy cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks AT dincamircea cationdependentintrinsicelectricalconductivityinisostructuraltetrathiafulvalenebasedmicroporousmetalorganicframeworks |