open access

https://hdl.handle.net/2115/91514

A Dualistic Arrangement of a Chiral [1]Rotaxane Based on the Assembly of Two Rings and Two Rods

英語

2023-04-07

American Chemical Society

Journal of organic chemistry

88(7)

4606-4618

We demonstrate the synthesis and chiroptical proper -ties of doubled molecules of a chiral [1]rotaxane, based on the assembly of an achiral ring of a phenylacetylene macrocycle (6PAM) and a p-phenylene ethynylene rod. Two molecules of [1]rotaxane constituted the doubled molecule through the ring fusion of 6PAMs to a 10PAM, which assured stationary occupation relative to each optically active unit. The absorption properties of the 10PAM-based doubled molecule and 6PAM-based original unit were consistently characterized by the independent existence of m-phenylene ethynylene ring(s) and p-phenylene ethynylene rod(s). Thus, molar circular dichroism (CD) was directly compared between the doubled molecule (n = 2) and the original unit (n = 1) to show that molar CD was increased more than expected by an increase in the number of units, or by an increase in absorbance. Due to the invariance of the configuration and the relative occupation of two units arranged adjacent to each other in 10PAM, one more comparison was available with an isomeric molecule of two rings and two rods in a threaded-and-unthreaded form. The additional arrangement of an optically inactive unit in an unthreaded form also led to an increase in molar CD, compared to that of the original chiral unit in a threaded form.

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Accepted Manuscript

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of organic chemistry copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-DZC8NNBK2IYNEJHDQJZT

0022-3263