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Substituent Control of σ-Interference Effects in the Transmission of Saturated Molecules

[Image: see text] The single-molecule conductance of saturated molecules can potentially be fully suppressed by destructive quantum interference in their σ-system. However, only few molecules with σ-interference have been identified, and the structure–property relationship remains to be elucidated....

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Detalles Bibliográficos
Autores principales: Garner, Marc H., Koerstz, Mads, Jensen, Jan H., Solomon, Gemma C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9955259/
https://www.ncbi.nlm.nih.gov/pubmed/36855417
http://dx.doi.org/10.1021/acsphyschemau.2c00016
Descripción
Sumario:[Image: see text] The single-molecule conductance of saturated molecules can potentially be fully suppressed by destructive quantum interference in their σ-system. However, only few molecules with σ-interference have been identified, and the structure–property relationship remains to be elucidated. Here, we explore the role of substituents in modulating the electronic transmission of saturated molecules. In functionalized bicyclo[2.2.2]octanes, the transmission is suppressed by σ-interference when fluorine substituents are applied. For bicyclo[2.2.2]octasilane and -octagermanes, the transmission is suppressed when carbon-based substituents are used, and such molecules are likely to be highly insulating. For the carbon-based substituents, we find a strong correlation between the appropriate Hammett constants and the transmission. The substituent effect enables systematic optimization of the insulating properties of saturated molecular cores.