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First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
Mercapto (–SH) and isocyano (–N[triple bond, length as m-dash]C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduc...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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Royal Society of Chemistry
2016
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4748958/ https://www.ncbi.nlm.nih.gov/pubmed/26877864 http://dx.doi.org/10.1039/c5sc04017e |
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author | Applegate, Jason C. Okeowo, Monisola K. Erickson, Nathan R. Neal, Brad M. Berrie, Cindy L. Gerasimchuk, Nikolay N. Barybin, Mikhail V. |
author_facet | Applegate, Jason C. Okeowo, Monisola K. Erickson, Nathan R. Neal, Brad M. Berrie, Cindy L. Gerasimchuk, Nikolay N. Barybin, Mikhail V. |
author_sort | Applegate, Jason C. |
collection | PubMed |
description | Mercapto (–SH) and isocyano (–N[triple bond, length as m-dash]C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic π-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N[triple bond, length as m-dash]C end of this 2,6-azulenic motif was anchrored to the [Cr(CO)(5)] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC)(5)Cr(η(1)-2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] (7) with Ph(3)PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr(0)/Au(I) ensemble [(OC)(5)Cr(μ-η(1):η(1)-2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh(3)] (8). Analysis of the (13)C NMR chemical shifts for the [(NC)Cr(CO)(5)] core in a series of the related complexes [(OC)(5)Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = –N[triple bond, length as m-dash]C, Br, H, SH, SCH(2)CH(2)CO(2)CH(2)CH(3), SAuPPh(3)) unveiled remarkably consistent inverse-linear correlations δ((13)CO(trans)) vs. δ((13)CN) and δ((13)CO(cis)) vs. δ((13)CN) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC)(5)Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF(3), CFClCF(2)Cl, C(2)F(3), and C(6)F(5). In addition to functioning as a sensitive (13)C NMR handle, the essentially C(4v)-symmetric [(–NC)Cr(CO)(5)] moiety proved to be an informative, remote, ν(N[triple bond, length as m-dash]C)/ν(C[triple bond, length as m-dash]O) infrared reporter in probing chemisorption of 7 on the Au(111) surface. |
format | Online Article Text |
id | pubmed-4748958 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-47489582017-02-01 First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111) Applegate, Jason C. Okeowo, Monisola K. Erickson, Nathan R. Neal, Brad M. Berrie, Cindy L. Gerasimchuk, Nikolay N. Barybin, Mikhail V. Chem Sci Chemistry Mercapto (–SH) and isocyano (–N[triple bond, length as m-dash]C) terminated conducting π-linkers are often employed in the ever-growing quest for organoelectronic materials. While such systems typically involve symmetric dimercapto or diisocyano anchoring of the organic bridge, this article introduces the chemistry of a linear azulenic π-linker equipped with one mercapto and one isocyano terminus. The 2-isocyano-6-mercaptoazulene platform was efficiently accessed from 2-amino-6-bromo-1,3-diethoxycarbonylazulene in four steps. The 2-N[triple bond, length as m-dash]C end of this 2,6-azulenic motif was anchrored to the [Cr(CO)(5)] fragment prior to formation of its 6-SH terminus. Metalation of the 6-SH end of [(OC)(5)Cr(η(1)-2-isocyano-1,3-diethoxycarbonyl-6-mercaptoazulene)] (7) with Ph(3)PAuCl, under basic conditions, afforded X-ray structurally characterized heterobimetallic Cr(0)/Au(I) ensemble [(OC)(5)Cr(μ-η(1):η(1)-2-isocyano-1,3-diethoxycarbonyl-6-azulenylthiolate)AuPPh(3)] (8). Analysis of the (13)C NMR chemical shifts for the [(NC)Cr(CO)(5)] core in a series of the related complexes [(OC)(5)Cr(2-isocyano-6-X-1,3-diethoxy-carbonylazulene)] (X = –N[triple bond, length as m-dash]C, Br, H, SH, SCH(2)CH(2)CO(2)CH(2)CH(3), SAuPPh(3)) unveiled remarkably consistent inverse-linear correlations δ((13)CO(trans)) vs. δ((13)CN) and δ((13)CO(cis)) vs. δ((13)CN) that appear to hold well beyond the above 2-isocyanoazulenic series to include complexes [(OC)(5)Cr(CNR)] containing strongly electron-withdrawing substituents R, such as CF(3), CFClCF(2)Cl, C(2)F(3), and C(6)F(5). In addition to functioning as a sensitive (13)C NMR handle, the essentially C(4v)-symmetric [(–NC)Cr(CO)(5)] moiety proved to be an informative, remote, ν(N[triple bond, length as m-dash]C)/ν(C[triple bond, length as m-dash]O) infrared reporter in probing chemisorption of 7 on the Au(111) surface. Royal Society of Chemistry 2016-02-01 2015-11-20 /pmc/articles/PMC4748958/ /pubmed/26877864 http://dx.doi.org/10.1039/c5sc04017e Text en This journal is © The Royal Society of Chemistry 2016 https://creativecommons.org/licenses/by/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) |
spellingShingle | Chemistry Applegate, Jason C. Okeowo, Monisola K. Erickson, Nathan R. Neal, Brad M. Berrie, Cindy L. Gerasimchuk, Nikolay N. Barybin, Mikhail V. First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111) |
title | First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
|
title_full | First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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title_fullStr | First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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title_full_unstemmed | First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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title_short | First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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title_sort | first π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on au(111) |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4748958/ https://www.ncbi.nlm.nih.gov/pubmed/26877864 http://dx.doi.org/10.1039/c5sc04017e |
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