Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Applegate, Jason C., Okeowo, Monisola K., Erickson, Nathan R., Neal, Brad M., Berrie, Cindy L., Gerasimchuk, Nikolay N., Barybin, Mikhail V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
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
_version_ 1782415208052948992
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)
title_fullStr First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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)
title_short First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)
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
work_keys_str_mv AT applegatejasonc firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT okeowomonisolak firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT ericksonnathanr firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT nealbradm firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT berriecindyl firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT gerasimchuknikolayn firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111
AT barybinmikhailv firstplinkerfeaturingmercaptoandisocyanoanchoringgroupswithinthesamemoleculesynthesisheterobimetalliccomplexationandselfassemblyonau111