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The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone

1,3-Dipolar cycloaddition of pyrido[2,1-a]isoindole with internal alkynes functionalized by a BMes(2)ph and an N-aromatic heterocycle leads to the formation of two types of regioisomers (major a and minor b) that have distinct physical and photophysical properties. Examination on 5 pairs of regioiso...

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Detalles Bibliográficos
Autores principales: Zeng, Chao, Yuan, Kang, Wang, Nan, Peng, Tai, Wu, Gang, Wang, Suning
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6369733/
https://www.ncbi.nlm.nih.gov/pubmed/30842837
http://dx.doi.org/10.1039/c8sc04210a
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author Zeng, Chao
Yuan, Kang
Wang, Nan
Peng, Tai
Wu, Gang
Wang, Suning
author_facet Zeng, Chao
Yuan, Kang
Wang, Nan
Peng, Tai
Wu, Gang
Wang, Suning
author_sort Zeng, Chao
collection PubMed
description 1,3-Dipolar cycloaddition of pyrido[2,1-a]isoindole with internal alkynes functionalized by a BMes(2)ph and an N-aromatic heterocycle leads to the formation of two types of regioisomers (major a and minor b) that have distinct physical and photophysical properties. Examination on 5 pairs of regioisomers unveils that the major isomers consistently have a smaller optical energy gap and emission energy than the corresponding minor isomers, which is greatly amplified by the formation of an internal B ← N bond. The regioisomers with a B ← N bond display contrasting temperature-dependent structural dynamics and response to fluoride ions, owing to an entropy-driven or fluoride initiated B ← N bond rupture/ring-opening process and the different B ← N bond strength. The opposite inductive effect and the Lewis pair properties of the dichotomic substituent units are responsible for the contrasting properties of the regioisomers in this system.
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spelling pubmed-63697332019-03-06 The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone Zeng, Chao Yuan, Kang Wang, Nan Peng, Tai Wu, Gang Wang, Suning Chem Sci Chemistry 1,3-Dipolar cycloaddition of pyrido[2,1-a]isoindole with internal alkynes functionalized by a BMes(2)ph and an N-aromatic heterocycle leads to the formation of two types of regioisomers (major a and minor b) that have distinct physical and photophysical properties. Examination on 5 pairs of regioisomers unveils that the major isomers consistently have a smaller optical energy gap and emission energy than the corresponding minor isomers, which is greatly amplified by the formation of an internal B ← N bond. The regioisomers with a B ← N bond display contrasting temperature-dependent structural dynamics and response to fluoride ions, owing to an entropy-driven or fluoride initiated B ← N bond rupture/ring-opening process and the different B ← N bond strength. The opposite inductive effect and the Lewis pair properties of the dichotomic substituent units are responsible for the contrasting properties of the regioisomers in this system. Royal Society of Chemistry 2018-11-29 /pmc/articles/PMC6369733/ /pubmed/30842837 http://dx.doi.org/10.1039/c8sc04210a Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Zeng, Chao
Yuan, Kang
Wang, Nan
Peng, Tai
Wu, Gang
Wang, Suning
The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title_full The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title_fullStr The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title_full_unstemmed The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title_short The opposite and amplifying effect of B ← N coordination on photophysical properties of regioisomers with an unsymmetrical backbone
title_sort opposite and amplifying effect of b ← n coordination on photophysical properties of regioisomers with an unsymmetrical backbone
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6369733/
https://www.ncbi.nlm.nih.gov/pubmed/30842837
http://dx.doi.org/10.1039/c8sc04210a
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