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Stereoselective gridization and polygridization with centrosymmetric molecular packing

The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic...

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Autores principales: Lin, Dongqing, Wei, Ying, Peng, Aizhong, Zhang, He, Zhong, Chunxiao, Lu, Dan, Zhang, Hao, Zheng, Xiangping, Yang, Lei, Feng, Quanyou, Xie, Linghai, Huang, Wei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7145858/
https://www.ncbi.nlm.nih.gov/pubmed/32273512
http://dx.doi.org/10.1038/s41467-020-15401-x
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author Lin, Dongqing
Wei, Ying
Peng, Aizhong
Zhang, He
Zhong, Chunxiao
Lu, Dan
Zhang, Hao
Zheng, Xiangping
Yang, Lei
Feng, Quanyou
Xie, Linghai
Huang, Wei
author_facet Lin, Dongqing
Wei, Ying
Peng, Aizhong
Zhang, He
Zhong, Chunxiao
Lu, Dan
Zhang, Hao
Zheng, Xiangping
Yang, Lei
Feng, Quanyou
Xie, Linghai
Huang, Wei
author_sort Lin, Dongqing
collection PubMed
description The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic diazafluorene-containing substrates (A(m)B(n)) with crescent shapes into Drawing Hands grids (DHGs). The meso-selectivity reaches 75.6% diastereomeric excess (de) during the gridization of A(1)B(1)-type substrates and maintains ~80% de during the polygridization of A(2)B(2)-type monomers. Such stereocontrol originates from the centrosymmetric molecular packing of two charge-delocalized superelectrophiles with synergistically π–π stacking attractions and coulombic repulsions. As meso-stereoregular structures show 20∼30 nm in length, the rigid ring/chain-alternating polygrids have a Mark–Houwink exponent of 1.651 and a molecular weight (M) dependence of the hydrodynamic radius R(h) ∼ M(1.13). Via the simulation of chain collapse, meso-configured polygridarenes still adopt rod-like conformations that facilitate the high rigidity of organic nanopolymers, distinguished from toroid backbones of rac-type polygrids.
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spelling pubmed-71458582020-04-13 Stereoselective gridization and polygridization with centrosymmetric molecular packing Lin, Dongqing Wei, Ying Peng, Aizhong Zhang, He Zhong, Chunxiao Lu, Dan Zhang, Hao Zheng, Xiangping Yang, Lei Feng, Quanyou Xie, Linghai Huang, Wei Nat Commun Article The gridarenes, with well-defined edges and vertices, represent versatile nanoscale building blocks for the installation of frameworks and architectures but suffer from difficulty in stereoselective control during their synthesis. Here we report a diastereoselective gridization of superelectrophilic diazafluorene-containing substrates (A(m)B(n)) with crescent shapes into Drawing Hands grids (DHGs). The meso-selectivity reaches 75.6% diastereomeric excess (de) during the gridization of A(1)B(1)-type substrates and maintains ~80% de during the polygridization of A(2)B(2)-type monomers. Such stereocontrol originates from the centrosymmetric molecular packing of two charge-delocalized superelectrophiles with synergistically π–π stacking attractions and coulombic repulsions. As meso-stereoregular structures show 20∼30 nm in length, the rigid ring/chain-alternating polygrids have a Mark–Houwink exponent of 1.651 and a molecular weight (M) dependence of the hydrodynamic radius R(h) ∼ M(1.13). Via the simulation of chain collapse, meso-configured polygridarenes still adopt rod-like conformations that facilitate the high rigidity of organic nanopolymers, distinguished from toroid backbones of rac-type polygrids. Nature Publishing Group UK 2020-04-09 /pmc/articles/PMC7145858/ /pubmed/32273512 http://dx.doi.org/10.1038/s41467-020-15401-x Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Lin, Dongqing
Wei, Ying
Peng, Aizhong
Zhang, He
Zhong, Chunxiao
Lu, Dan
Zhang, Hao
Zheng, Xiangping
Yang, Lei
Feng, Quanyou
Xie, Linghai
Huang, Wei
Stereoselective gridization and polygridization with centrosymmetric molecular packing
title Stereoselective gridization and polygridization with centrosymmetric molecular packing
title_full Stereoselective gridization and polygridization with centrosymmetric molecular packing
title_fullStr Stereoselective gridization and polygridization with centrosymmetric molecular packing
title_full_unstemmed Stereoselective gridization and polygridization with centrosymmetric molecular packing
title_short Stereoselective gridization and polygridization with centrosymmetric molecular packing
title_sort stereoselective gridization and polygridization with centrosymmetric molecular packing
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7145858/
https://www.ncbi.nlm.nih.gov/pubmed/32273512
http://dx.doi.org/10.1038/s41467-020-15401-x
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