Tuning Antiaromaticity Through Meso-Substituent Orientation in Core-Modified Isophlorins

Isoda, Maika; Sugimura, Haruna; Honda, Yusuke et al.

Asian Journal of Organic Chemistry, 2025, e00372

Number of Access:16（2025-08-28 17:32 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/102229

Link to primary information 

File Format Terms of use Size Views Date.Available Description information
AsianJournalofOrganicChemistry_e00372 pdf None 2.30 MB 10 2025.07.10  
Creative Commons : Attribution - NonCommercial

Item Information

Output File Export EndNote Basic Export Mendeley

Title
Tuning Antiaromaticity Through Meso-Substituent Orientation in Core-Modified Isophlorins
Creator
CreatorName
Isoda, Maika
ORCID
0000-0002-7394-2838 0000-0002-7394-2838
CreatorName
Sugimura, Haruna
CreatorName
Honda, Yusuke
NRID
1000040468145 1000040468145
ORCID
0000-0001-7270-1234 0000-0001-7270-1234
researchmap permalink
ken1-yamashi ken1-yamashi
Scopus Author ID
35792834600 35792834600
CreatorName
Yamashita, Ken ichi
Subject
Antiaromaticity
Computational Chemistry
Isophlorin
Porphyrinoids
Substituent Effects
Description
Isoda M., Sugimura H., Honda Y., et al. Tuning Antiaromaticity Through Meso-Substituent Orientation in Core-Modified Isophlorins. Asian Journal of Organic Chemistry , (2025); https://doi.org/10.1002/ajoc.202500372.
Abstract
Antiaromaticity is an essential principle in organic chemistry that significantly influences the properties of cyclic π-conjugated systems. This study systematically investigated the effects of meso-substituents on the antiaromaticity of dithiadioxaisophlorins (S₂O₂Iphs), which are stable isophlorin derivatives with strong antiaromatic characteristics. We synthesized two new S₂O₂Iphs derivatives with 3,5-bis(trifluoromethyl)phenyl and 5-cyanothien-2-yl substituents along with a previously reported pentafluorophenyl-substituted analog. Notably, a derivative with sterically demanding 2,6-dichlorophenyl substituents could not be isolated despite being detected by mass spectrometry, highlighting the delicate balance between electronic stabilization, and steric effects. Through comprehensive analysis using ¹H NMR spectroscopy, UV/vis absorption spectroscopy, and multiple computational approaches (NICS, GIMIC, HOMA/HOMAc, and AV1245/AVₘᵢₙ), we demonstrate that the steric bulkiness of meso-substituents predominantly determines their tilt angle relative to the isophlorin macrocycle, critically influencing antiaromaticity. Bulkier substituents maintain larger tilt angles, preserving stronger antiaromaticity, while less bulky groups allow greater π-conjugation with the macrocycle, thereby reducing antiaromaticity. These findings provide valuable guidance for the design of functional antiaromatic materials with tunable electronic properties.
Publisher
John Wiley and Sons Inc
Source Title
Asian Journal of Organic Chemistry
Page
e00372
Date of Issued
2025-05-22
Language
English
Handle URL
https://hdl.handle.net/11094/102229
PISSN
21935807
eISSN
21935815
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1002/ajoc.202500372
Access Rights
open access
CopyRight
© 2025 The Author(s). Asian Journal of Organic Chemistry published by Wiley-VCH GmbH.
This article is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
oaire:version
Version of Record
Category
学術雑誌論文 Journal Article