Cargando…
Charging OBO‐Fused Double [5]Helicene with Electrons
Chemical reduction of OBO‐fused double[5]helicene with Group 1 metals (Na and K) has been investigated for the first time. Two doubly‐reduced products have been isolated and structurally characterized by single‐crystal X‐ray diffraction, revealing a solvent‐separated ion triplet (SSIT) with Na(+) io...
Autores principales: | , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2019
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916263/ https://www.ncbi.nlm.nih.gov/pubmed/31430019 http://dx.doi.org/10.1002/anie.201908658 |
_version_ | 1783480196124377088 |
---|---|
author | Zhou, Zheng Wang, Xiao‐Ye Wei, Zheng Müllen, Klaus Petrukhina, Marina A. |
author_facet | Zhou, Zheng Wang, Xiao‐Ye Wei, Zheng Müllen, Klaus Petrukhina, Marina A. |
author_sort | Zhou, Zheng |
collection | PubMed |
description | Chemical reduction of OBO‐fused double[5]helicene with Group 1 metals (Na and K) has been investigated for the first time. Two doubly‐reduced products have been isolated and structurally characterized by single‐crystal X‐ray diffraction, revealing a solvent‐separated ion triplet (SSIT) with Na(+) ions and a contact‐ion pair (CIP) with K(+) ion. As the key structural outcome, the X‐ray crystallographic analysis discloses the consequences of adding two electrons to the double helicene core in the SSIT without metal binding and reveals the preferential binding site in the CIP with K(+) counterions. In both products, an increase in the twisting of the double helicene core upon charging was observed. The negative charge localization at the central core has been identified by theoretical calculations, which are in full agreement with X‐ray crystallographic and NMR spectroscopic results. Notably, it was confirmed that the two‐electron reduction of OBO‐fused double[5]helicene is reversible. |
format | Online Article Text |
id | pubmed-6916263 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-69162632019-12-17 Charging OBO‐Fused Double [5]Helicene with Electrons Zhou, Zheng Wang, Xiao‐Ye Wei, Zheng Müllen, Klaus Petrukhina, Marina A. Angew Chem Int Ed Engl Communications Chemical reduction of OBO‐fused double[5]helicene with Group 1 metals (Na and K) has been investigated for the first time. Two doubly‐reduced products have been isolated and structurally characterized by single‐crystal X‐ray diffraction, revealing a solvent‐separated ion triplet (SSIT) with Na(+) ions and a contact‐ion pair (CIP) with K(+) ion. As the key structural outcome, the X‐ray crystallographic analysis discloses the consequences of adding two electrons to the double helicene core in the SSIT without metal binding and reveals the preferential binding site in the CIP with K(+) counterions. In both products, an increase in the twisting of the double helicene core upon charging was observed. The negative charge localization at the central core has been identified by theoretical calculations, which are in full agreement with X‐ray crystallographic and NMR spectroscopic results. Notably, it was confirmed that the two‐electron reduction of OBO‐fused double[5]helicene is reversible. John Wiley and Sons Inc. 2019-09-09 2019-10-14 /pmc/articles/PMC6916263/ /pubmed/31430019 http://dx.doi.org/10.1002/anie.201908658 Text en ©2019 The Authors published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Zhou, Zheng Wang, Xiao‐Ye Wei, Zheng Müllen, Klaus Petrukhina, Marina A. Charging OBO‐Fused Double [5]Helicene with Electrons |
title | Charging OBO‐Fused Double [5]Helicene with Electrons |
title_full | Charging OBO‐Fused Double [5]Helicene with Electrons |
title_fullStr | Charging OBO‐Fused Double [5]Helicene with Electrons |
title_full_unstemmed | Charging OBO‐Fused Double [5]Helicene with Electrons |
title_short | Charging OBO‐Fused Double [5]Helicene with Electrons |
title_sort | charging obo‐fused double [5]helicene with electrons |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916263/ https://www.ncbi.nlm.nih.gov/pubmed/31430019 http://dx.doi.org/10.1002/anie.201908658 |
work_keys_str_mv | AT zhouzheng chargingobofuseddouble5helicenewithelectrons AT wangxiaoye chargingobofuseddouble5helicenewithelectrons AT weizheng chargingobofuseddouble5helicenewithelectrons AT mullenklaus chargingobofuseddouble5helicenewithelectrons AT petrukhinamarinaa chargingobofuseddouble5helicenewithelectrons |