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Charge Transport Across Dynamic Covalent Chemical Bridges
[Image: see text] Relationships between chemical structure and conductivity in ordered polymers (OPs) are difficult to probe using bulk samples. We propose that conductance measurements of appropriate molecular-scale models can reveal trends in electronic coupling(s) between repeat units that may he...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9614958/ https://www.ncbi.nlm.nih.gov/pubmed/36215246 http://dx.doi.org/10.1021/acs.nanolett.2c03288 |
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author | Miao, Zelin Quainoo, Timothy Czyszczon-Burton, Thomas M. Rotthowe, Nils Parr, Joseph M. Liu, Zhen-Fei Inkpen, Michael S. |
author_facet | Miao, Zelin Quainoo, Timothy Czyszczon-Burton, Thomas M. Rotthowe, Nils Parr, Joseph M. Liu, Zhen-Fei Inkpen, Michael S. |
author_sort | Miao, Zelin |
collection | PubMed |
description | [Image: see text] Relationships between chemical structure and conductivity in ordered polymers (OPs) are difficult to probe using bulk samples. We propose that conductance measurements of appropriate molecular-scale models can reveal trends in electronic coupling(s) between repeat units that may help inform OP design. Here, we apply the scanning tunneling microscope-based break-junction (STM-BJ) method to study transport through single-molecules comprising OP-relevant imine, imidazole, diazaborole, and boronate ester dynamic covalent chemical bridges. Notably, solution-stable boron-based compounds dissociate in situ unless measured under a rigorously inert glovebox atmosphere. We find that junction conductance negatively correlates with the electronegativity difference between bridge atoms, and corroborative first-principles calculations further reveal a different nodal structure in the transmission eigenchannels of boronate ester junctions. This work reaffirms expectations that highly polarized bridge motifs represent poor choices for the construction of OPs with high through-bond conductivity and underscores the utility of glovebox STM-BJ instrumentation for studies of air-sensitive materials. |
format | Online Article Text |
id | pubmed-9614958 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-96149582022-10-29 Charge Transport Across Dynamic Covalent Chemical Bridges Miao, Zelin Quainoo, Timothy Czyszczon-Burton, Thomas M. Rotthowe, Nils Parr, Joseph M. Liu, Zhen-Fei Inkpen, Michael S. Nano Lett [Image: see text] Relationships between chemical structure and conductivity in ordered polymers (OPs) are difficult to probe using bulk samples. We propose that conductance measurements of appropriate molecular-scale models can reveal trends in electronic coupling(s) between repeat units that may help inform OP design. Here, we apply the scanning tunneling microscope-based break-junction (STM-BJ) method to study transport through single-molecules comprising OP-relevant imine, imidazole, diazaborole, and boronate ester dynamic covalent chemical bridges. Notably, solution-stable boron-based compounds dissociate in situ unless measured under a rigorously inert glovebox atmosphere. We find that junction conductance negatively correlates with the electronegativity difference between bridge atoms, and corroborative first-principles calculations further reveal a different nodal structure in the transmission eigenchannels of boronate ester junctions. This work reaffirms expectations that highly polarized bridge motifs represent poor choices for the construction of OPs with high through-bond conductivity and underscores the utility of glovebox STM-BJ instrumentation for studies of air-sensitive materials. American Chemical Society 2022-10-10 2022-10-26 /pmc/articles/PMC9614958/ /pubmed/36215246 http://dx.doi.org/10.1021/acs.nanolett.2c03288 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Miao, Zelin Quainoo, Timothy Czyszczon-Burton, Thomas M. Rotthowe, Nils Parr, Joseph M. Liu, Zhen-Fei Inkpen, Michael S. Charge Transport Across Dynamic Covalent Chemical Bridges |
title | Charge Transport
Across Dynamic Covalent Chemical
Bridges |
title_full | Charge Transport
Across Dynamic Covalent Chemical
Bridges |
title_fullStr | Charge Transport
Across Dynamic Covalent Chemical
Bridges |
title_full_unstemmed | Charge Transport
Across Dynamic Covalent Chemical
Bridges |
title_short | Charge Transport
Across Dynamic Covalent Chemical
Bridges |
title_sort | charge transport
across dynamic covalent chemical
bridges |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9614958/ https://www.ncbi.nlm.nih.gov/pubmed/36215246 http://dx.doi.org/10.1021/acs.nanolett.2c03288 |
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