Introducing a π‐Skeleton Perpendicular to the Central Methylene Carbon in Alkanediamides: Design of Supramolecular Polymers with an Offset π‐Stacking Arrangement

Author:

Hamada Yasuhiro1,Ogi Soichiro2ORCID,Yamaguchi Shigehiro123ORCID

Affiliation:

1. Department of Chemistry, Graduate School of Science Nagoya University Furo, Chikusa Nagoya 464-8602 Japan

2. Integrated Research Consortium on Chemical Science (IRCCS) Nagoya University Furo, Chikusa Nagoya 464-8602 Japan

3. Institute of Transformative Bio-Molecules (WPI-ITbM) Nagoya University Furo, Chikusa Nagoya 464-8602 Japan

Abstract

AbstractThe self‐assembly behavior of a heptanediamide derivative that contains a four‐ring fused π‐skeleton on its central methylene carbon atom has been examined. This molecule, which also contains two octyl chains, gelated the nonpolar solvent methylcyclohexane through the formation of fibrous nanostructures with hydrogen‐bonding networks through a cooperative nucleation–elongation process. The supramolecular polymerization is accompanied by bathochromic shifts of both the absorption and fluorescence bands while maintaining a fluorescence quantum yield comparable to that of the monomeric state. Theoretical calculations provided an energetically stable structure, in which the π‐skeletons are stacked with an offset of more than 8.0 Å, replicating the experimentally observed absorption change due to exciton coupling. Moreover, a slow transition with an inversion of the chiral arrangement of the π‐conjugated moieties was induced by replacing the octyl chains with chiral alkyl chains. Our molecular‐design strategy was further applied to a five‐ring fused π‐skeleton, which also forms an offset π‐stacking arrangement and exhibits more effective chiral exciton coupling in the aggregated state.

Funder

Japan Society for the Promotion of Science

Core Research for Evolutional Science and Technology

Publisher

Wiley

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3