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Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization
We report the synthesis of a new bistriarylamine series having a urea bridge and investigate its mixed-valence (MV) states by electrochemical and spectroelectrochemical methods. We found that the supporting electrolytes had unusual effects on potential splitting during electrochemical behavior, in w...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6774064/ https://www.ncbi.nlm.nih.gov/pubmed/31598180 http://dx.doi.org/10.3762/bjoc.15.220 |
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author | Tahara, Keishiro Nakakita, Tetsufumi Starikova, Alyona A Ikeda, Takashi Abe, Masaaki Kikuchi, Jun-ichi |
author_facet | Tahara, Keishiro Nakakita, Tetsufumi Starikova, Alyona A Ikeda, Takashi Abe, Masaaki Kikuchi, Jun-ichi |
author_sort | Tahara, Keishiro |
collection | PubMed |
description | We report the synthesis of a new bistriarylamine series having a urea bridge and investigate its mixed-valence (MV) states by electrochemical and spectroelectrochemical methods. We found that the supporting electrolytes had unusual effects on potential splitting during electrochemical behavior, in which a smaller counteranion thermodynamically stabilized a MV cation more substantially than did a bulky one. The effects contrary to those reported in conventional MV systems were explained by zwitterionization through hydrogen bonding between the urea bridge and the counteranions, increasing the electronic interactions between two triarylamino units. Furthermore, we clarified the intervalence charge transfer characteristics of the zwitterionic MV state. |
format | Online Article Text |
id | pubmed-6774064 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Beilstein-Institut |
record_format | MEDLINE/PubMed |
spelling | pubmed-67740642019-10-09 Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization Tahara, Keishiro Nakakita, Tetsufumi Starikova, Alyona A Ikeda, Takashi Abe, Masaaki Kikuchi, Jun-ichi Beilstein J Org Chem Full Research Paper We report the synthesis of a new bistriarylamine series having a urea bridge and investigate its mixed-valence (MV) states by electrochemical and spectroelectrochemical methods. We found that the supporting electrolytes had unusual effects on potential splitting during electrochemical behavior, in which a smaller counteranion thermodynamically stabilized a MV cation more substantially than did a bulky one. The effects contrary to those reported in conventional MV systems were explained by zwitterionization through hydrogen bonding between the urea bridge and the counteranions, increasing the electronic interactions between two triarylamino units. Furthermore, we clarified the intervalence charge transfer characteristics of the zwitterionic MV state. Beilstein-Institut 2019-09-24 /pmc/articles/PMC6774064/ /pubmed/31598180 http://dx.doi.org/10.3762/bjoc.15.220 Text en Copyright © 2019, Tahara et al. https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms) |
spellingShingle | Full Research Paper Tahara, Keishiro Nakakita, Tetsufumi Starikova, Alyona A Ikeda, Takashi Abe, Masaaki Kikuchi, Jun-ichi Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title | Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title_full | Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title_fullStr | Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title_full_unstemmed | Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title_short | Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
title_sort | small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization |
topic | Full Research Paper |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6774064/ https://www.ncbi.nlm.nih.gov/pubmed/31598180 http://dx.doi.org/10.3762/bjoc.15.220 |
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