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Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives
[Image: see text] Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H(4)TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning the synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9136926/ https://www.ncbi.nlm.nih.gov/pubmed/35575688 http://dx.doi.org/10.1021/jacs.2c01957 |
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author | Vicent-Morales, María Esteve-Rochina, María Calbo, Joaquín Ortí, Enrique Vitórica-Yrezábal, Iñigo J. Mínguez Espallargas, Guillermo |
author_facet | Vicent-Morales, María Esteve-Rochina, María Calbo, Joaquín Ortí, Enrique Vitórica-Yrezábal, Iñigo J. Mínguez Espallargas, Guillermo |
author_sort | Vicent-Morales, María |
collection | PubMed |
description | [Image: see text] Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H(4)TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning the synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21, all of them presenting open structures (22, 15, and 27%, respectively) and suitable TTF stacking for efficient orbital overlap. Whereas MUV-21 collapses during the activation process, MUV-20a and MUV-20b offer high stability evacuation, with a CO(2) sorption capacity of 1.91 and 1.71 mmol g(–1), respectively, at 10 °C and 6 bar. Interestingly, both MUV-20a and MUV-20b present a zwitterionic character with a positively charged TTF core and a negatively charged carboxylate group. First-principles calculations predict the emergence of remarkable charge transport by means of a through-space hopping mechanism fostered by an efficient TTF π–π stacking and the spontaneous formation of persistent charge carriers in the form of radical TTF(•+) units. Transport measurements confirm the efficient charge transport in zwitterionic MUV-20a and MUV-20b with no need for postsynthetic treatment (e.g., electrochemical oxidation or doping), demonstrating the semiconductor nature of these HOFs with record experimental conductivities of 6.07 × 10(–7) (MUV-20a) and 1.35 × 10(–6) S cm(–1) (MUV-20b). |
format | Online Article Text |
id | pubmed-9136926 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-91369262022-05-28 Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives Vicent-Morales, María Esteve-Rochina, María Calbo, Joaquín Ortí, Enrique Vitórica-Yrezábal, Iñigo J. Mínguez Espallargas, Guillermo J Am Chem Soc [Image: see text] Herein, we report on the use of tetrathiavulvalene-tetrabenzoic acid, H(4)TTFTB, to engender semiconductivity in porous hydrogen-bonded organic frameworks (HOFs). By tuning the synthetic conditions, three different polymorphs have been obtained, denoted MUV-20a, MUV-20b, and MUV-21, all of them presenting open structures (22, 15, and 27%, respectively) and suitable TTF stacking for efficient orbital overlap. Whereas MUV-21 collapses during the activation process, MUV-20a and MUV-20b offer high stability evacuation, with a CO(2) sorption capacity of 1.91 and 1.71 mmol g(–1), respectively, at 10 °C and 6 bar. Interestingly, both MUV-20a and MUV-20b present a zwitterionic character with a positively charged TTF core and a negatively charged carboxylate group. First-principles calculations predict the emergence of remarkable charge transport by means of a through-space hopping mechanism fostered by an efficient TTF π–π stacking and the spontaneous formation of persistent charge carriers in the form of radical TTF(•+) units. Transport measurements confirm the efficient charge transport in zwitterionic MUV-20a and MUV-20b with no need for postsynthetic treatment (e.g., electrochemical oxidation or doping), demonstrating the semiconductor nature of these HOFs with record experimental conductivities of 6.07 × 10(–7) (MUV-20a) and 1.35 × 10(–6) S cm(–1) (MUV-20b). American Chemical Society 2022-05-16 2022-05-25 /pmc/articles/PMC9136926/ /pubmed/35575688 http://dx.doi.org/10.1021/jacs.2c01957 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Vicent-Morales, María Esteve-Rochina, María Calbo, Joaquín Ortí, Enrique Vitórica-Yrezábal, Iñigo J. Mínguez Espallargas, Guillermo Semiconductor Porous Hydrogen-Bonded Organic Frameworks Based on Tetrathiafulvalene Derivatives |
title | Semiconductor
Porous Hydrogen-Bonded Organic Frameworks
Based on Tetrathiafulvalene Derivatives |
title_full | Semiconductor
Porous Hydrogen-Bonded Organic Frameworks
Based on Tetrathiafulvalene Derivatives |
title_fullStr | Semiconductor
Porous Hydrogen-Bonded Organic Frameworks
Based on Tetrathiafulvalene Derivatives |
title_full_unstemmed | Semiconductor
Porous Hydrogen-Bonded Organic Frameworks
Based on Tetrathiafulvalene Derivatives |
title_short | Semiconductor
Porous Hydrogen-Bonded Organic Frameworks
Based on Tetrathiafulvalene Derivatives |
title_sort | semiconductor
porous hydrogen-bonded organic frameworks
based on tetrathiafulvalene derivatives |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9136926/ https://www.ncbi.nlm.nih.gov/pubmed/35575688 http://dx.doi.org/10.1021/jacs.2c01957 |
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