Local probe-induced structural isomerization in a one-dimensional molecular array
Abstract Synthesis of one-dimensional molecular arrays with tailored stereoisomers is challenging yet has great potential for application in molecular opto-, electronic- and magnetic-devices, where the local array structure plays a decisive role in the functional properties. Here, we demonstrate the...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-43659-4 |
| _version_ | 1797452112925294592 |
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| author | Shigeki Kawai Orlando J. Silveira Lauri Kurki Zhangyu Yuan Tomohiko Nishiuchi Takuya Kodama Kewei Sun Oscar Custance Jose L. Lado Takashi Kubo Adam S. Foster |
| author_facet | Shigeki Kawai Orlando J. Silveira Lauri Kurki Zhangyu Yuan Tomohiko Nishiuchi Takuya Kodama Kewei Sun Oscar Custance Jose L. Lado Takashi Kubo Adam S. Foster |
| author_sort | Shigeki Kawai |
| collection | DOAJ |
| description | Abstract Synthesis of one-dimensional molecular arrays with tailored stereoisomers is challenging yet has great potential for application in molecular opto-, electronic- and magnetic-devices, where the local array structure plays a decisive role in the functional properties. Here, we demonstrate the construction and characterization of dehydroazulene isomer and diradical units in three-dimensional organometallic compounds on Ag(111) with a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. Tip-induced voltage pulses firstly result in the formation of a diradical species via successive homolytic fission of two C-Br bonds in the naphthyl groups, which are subsequently transformed into chiral dehydroazulene moieties. The delicate balance of the reaction rates among the diradical and two stereoisomers, arising from an in-line configuration of tip and molecular unit, allows directional azulene-to-azulene and azulene-to-diradical local probe structural isomerization in a controlled manner. Furthermore, our theoretical calculations suggest that the diradical moiety hosts an open-shell singlet with antiferromagnetic coupling between the unpaired electrons, which can undergo an inelastic spin transition of 91 meV to the ferromagnetically coupled triplet state. |
| first_indexed | 2024-03-09T15:04:05Z |
| format | Article |
| id | doaj.art-83d4e3453c5e4997a1b1f5ddc8c88478 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-09T15:04:05Z |
| publishDate | 2023-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-83d4e3453c5e4997a1b1f5ddc8c884782023-11-26T13:44:46ZengNature PortfolioNature Communications2041-17232023-11-011411710.1038/s41467-023-43659-4Local probe-induced structural isomerization in a one-dimensional molecular arrayShigeki Kawai0Orlando J. Silveira1Lauri Kurki2Zhangyu Yuan3Tomohiko Nishiuchi4Takuya Kodama5Kewei Sun6Oscar Custance7Jose L. Lado8Takashi Kubo9Adam S. Foster10Center for Basic Research on Materials, National Institute for Materials ScienceDepartment of Applied Physics, Aalto UniversityDepartment of Applied Physics, Aalto UniversityCenter for Basic Research on Materials, National Institute for Materials ScienceDepartment of Chemistry, Graduate School of Science, Osaka UniversityDepartment of Chemistry, Graduate School of Science, Osaka UniversityCenter for Basic Research on Materials, National Institute for Materials ScienceCenter for Basic Research on Materials, National Institute for Materials ScienceDepartment of Applied Physics, Aalto UniversityDepartment of Chemistry, Graduate School of Science, Osaka UniversityDepartment of Applied Physics, Aalto UniversityAbstract Synthesis of one-dimensional molecular arrays with tailored stereoisomers is challenging yet has great potential for application in molecular opto-, electronic- and magnetic-devices, where the local array structure plays a decisive role in the functional properties. Here, we demonstrate the construction and characterization of dehydroazulene isomer and diradical units in three-dimensional organometallic compounds on Ag(111) with a combination of low-temperature scanning tunneling microscopy and density functional theory calculations. Tip-induced voltage pulses firstly result in the formation of a diradical species via successive homolytic fission of two C-Br bonds in the naphthyl groups, which are subsequently transformed into chiral dehydroazulene moieties. The delicate balance of the reaction rates among the diradical and two stereoisomers, arising from an in-line configuration of tip and molecular unit, allows directional azulene-to-azulene and azulene-to-diradical local probe structural isomerization in a controlled manner. Furthermore, our theoretical calculations suggest that the diradical moiety hosts an open-shell singlet with antiferromagnetic coupling between the unpaired electrons, which can undergo an inelastic spin transition of 91 meV to the ferromagnetically coupled triplet state.https://doi.org/10.1038/s41467-023-43659-4 |
| spellingShingle | Shigeki Kawai Orlando J. Silveira Lauri Kurki Zhangyu Yuan Tomohiko Nishiuchi Takuya Kodama Kewei Sun Oscar Custance Jose L. Lado Takashi Kubo Adam S. Foster Local probe-induced structural isomerization in a one-dimensional molecular array Nature Communications |
| title | Local probe-induced structural isomerization in a one-dimensional molecular array |
| title_full | Local probe-induced structural isomerization in a one-dimensional molecular array |
| title_fullStr | Local probe-induced structural isomerization in a one-dimensional molecular array |
| title_full_unstemmed | Local probe-induced structural isomerization in a one-dimensional molecular array |
| title_short | Local probe-induced structural isomerization in a one-dimensional molecular array |
| title_sort | local probe induced structural isomerization in a one dimensional molecular array |
| url | https://doi.org/10.1038/s41467-023-43659-4 |
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