Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Tahara, Keishiro, Nakakita, Tetsufumi, Starikova, Alyona A, Ikeda, Takashi, Abe, Masaaki, Kikuchi, Jun-ichi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2019
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
_version_ 1783456030270685184
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
work_keys_str_mv AT taharakeishiro smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization
AT nakakitatetsufumi smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization
AT starikovaalyonaa smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization
AT ikedatakashi smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization
AT abemasaaki smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization
AT kikuchijunichi smallanionassistedelectrochemicalpotentialsplittinginanewseriesofbistriarylaminederivativesorganicmixedvalencyacrossaureabridgeandzwitterionization