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Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity
Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) (isoBBT) is a new electron-withdrawing building block that can be used to obtain potentially interesting compounds for the synthesis of OLEDs and organic solar cells components. The electronic structure and delocalization in benzo[1,2-d:4,5-d′]bis([1,2,3]th...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10219027/ https://www.ncbi.nlm.nih.gov/pubmed/37240184 http://dx.doi.org/10.3390/ijms24108835 |
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author | Chmovzh, Timofey N. Alekhina, Daria A. Kudryashev, Timofey A. Aysin, Rinat R. Korlyukov, Alexander A. Rakitin, Oleg A. |
author_facet | Chmovzh, Timofey N. Alekhina, Daria A. Kudryashev, Timofey A. Aysin, Rinat R. Korlyukov, Alexander A. Rakitin, Oleg A. |
author_sort | Chmovzh, Timofey N. |
collection | PubMed |
description | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) (isoBBT) is a new electron-withdrawing building block that can be used to obtain potentially interesting compounds for the synthesis of OLEDs and organic solar cells components. The electronic structure and delocalization in benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), and 4,8-dibromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) were studied using X-ray diffraction analysis and ab initio calculations by EDDB and GIMIC methods and were compared to the corresponding properties of benzo[1,2-c:4,5-c′]bis[1,2,5]thiadiazole (BBT). Calculations at a high level of theory showed that the electron affinity, which determines electron deficiency, of isoBBT was significantly smaller than that of BBT (1.09 vs. 1.90 eV). Incorporation of bromine atoms improves the electrical deficiency of bromobenzo-bis-thiadiazoles nearly without affecting aromaticity, which increases the reactivity of these compounds in aromatic nucleophilic substitution reactions and, on the other hand, does not reduce the ability to undergo cross-coupling reactions. 4-Bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) is an attractive object for the synthesis of monosubstituted isoBBT compounds. The goal to find conditions for the selective substitution of hydrogen or bromine atoms at position 4 in order to obtain compounds containing a (het)aryl group in this position and to use the remaining unsubstituted hydrogen or bromine atoms to obtain unsymmetrically substituted isoBBT derivatives, potentially interesting compounds for organic photovoltaic components, was not set before. Nucleophilic aromatic and cross-coupling reactions, along with palladium-catalyzed C-H direct arylation reactions for 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), were studied and selective conditions for the synthesis of monoarylated derivatives were found. The observed features of the structure and reactivity of isoBBT derivatives may be useful for building organic semiconductor-based devices. |
format | Online Article Text |
id | pubmed-10219027 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-102190272023-05-27 Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity Chmovzh, Timofey N. Alekhina, Daria A. Kudryashev, Timofey A. Aysin, Rinat R. Korlyukov, Alexander A. Rakitin, Oleg A. Int J Mol Sci Article Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) (isoBBT) is a new electron-withdrawing building block that can be used to obtain potentially interesting compounds for the synthesis of OLEDs and organic solar cells components. The electronic structure and delocalization in benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), and 4,8-dibromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) were studied using X-ray diffraction analysis and ab initio calculations by EDDB and GIMIC methods and were compared to the corresponding properties of benzo[1,2-c:4,5-c′]bis[1,2,5]thiadiazole (BBT). Calculations at a high level of theory showed that the electron affinity, which determines electron deficiency, of isoBBT was significantly smaller than that of BBT (1.09 vs. 1.90 eV). Incorporation of bromine atoms improves the electrical deficiency of bromobenzo-bis-thiadiazoles nearly without affecting aromaticity, which increases the reactivity of these compounds in aromatic nucleophilic substitution reactions and, on the other hand, does not reduce the ability to undergo cross-coupling reactions. 4-Bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) is an attractive object for the synthesis of monosubstituted isoBBT compounds. The goal to find conditions for the selective substitution of hydrogen or bromine atoms at position 4 in order to obtain compounds containing a (het)aryl group in this position and to use the remaining unsubstituted hydrogen or bromine atoms to obtain unsymmetrically substituted isoBBT derivatives, potentially interesting compounds for organic photovoltaic components, was not set before. Nucleophilic aromatic and cross-coupling reactions, along with palladium-catalyzed C-H direct arylation reactions for 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), were studied and selective conditions for the synthesis of monoarylated derivatives were found. The observed features of the structure and reactivity of isoBBT derivatives may be useful for building organic semiconductor-based devices. MDPI 2023-05-16 /pmc/articles/PMC10219027/ /pubmed/37240184 http://dx.doi.org/10.3390/ijms24108835 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Chmovzh, Timofey N. Alekhina, Daria A. Kudryashev, Timofey A. Aysin, Rinat R. Korlyukov, Alexander A. Rakitin, Oleg A. Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title_full | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title_fullStr | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title_full_unstemmed | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title_short | Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and Its Bromo Derivatives: Molecular Structure and Reactivity |
title_sort | benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) and its bromo derivatives: molecular structure and reactivity |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10219027/ https://www.ncbi.nlm.nih.gov/pubmed/37240184 http://dx.doi.org/10.3390/ijms24108835 |
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