Reversing the Bond Length Alternation Order in Conjugated Polyenes by Substituent Effects.
Publisher DOI
PubMed ID
36515459
Abstract
We have synthesised several push-pull substituted conjugated polyenes and determined their accurate C-C bond lengths and charge-density distribution by utilising quantum crystallographic techniques. In a series of alkene, diene, and triene bearing two (trifluoromethyl)sulfonyl (triflyl) groups on the terminal carbon atom, unique reversal of the bond-length alternation (BLA) order has been observed. This is a pronounced aberration from the molecular structure predicted by the Lewis structure-based neutral resonance structure. Such reversal of BLA order has not been observed in push-pull compounds bearing conventional electron-withdrawing groups such as carbonyl and cyano groups instead of triflyl groups. Bonding behaviour of both normal and reversed bond length alternating systems has been revealed by complementary bonding analysis using several bond descriptors based on the experimentally fitted wavefunctions.
Date Issued
2023-03-13
Publication Type
Article
Subject(s)
Subjects
bond alternations bond lengths complementary bonding analysis polyenes quantum crystallography
Language(s)
en
Author(s)
Yanai, Hikaru | |
Terajima, Yoshihiko | |
Kleemiss, Florian | |
Matsumoto, Takashi |
Additional Credits
Journal
Chemistry: a European journal
Publisher
Wiley
ISSN
1521-3765
Access(Rights)
open.access