Through-Bond and Through-Space Interactions of Organic Radicals Coupled by m-Phenylene

Kazunari Yoshizawa, Takao Kuga, Tohru Sato, Masashi Hatanaka, Kazuyoshi Tanaka, Tokio Yamabe

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Through-bond and through-space magnetic interactions in tricarbene and its related triradicals coupled through m-phenylene units are discussed with a semiempirical molecular orbital method including configuration interactions (PM3-CI method). The high-spin (HS) and low-spin (LS) states have quite similar geometries, but the methylene bridging angle is larger in the HS states. The HS states of these lie well below the corresponding LS states, except for one which contains nitroxide and aminiumyl radicals. Instability of the HS state of the heteroatomic system is a consequence of significant mixing between NBMOs and benzene elg-type orbitals, which can be explained in terms of simple perturbation theory. The energy difference between the HS and LS states is not explicitly influenced by the conformation of the molecules examined. This shows that such conformations have little effect on the magnetic properties in possible polymer ferromagnets which contain m-phenylene coupling units, as far as the second nearest neighbor interaction.

Original languageEnglish
Pages (from-to)3443-3450
Number of pages8
JournalBulletin of the Chemical Society of Japan
Volume69
Issue number12
DOIs
Publication statusPublished - Dec 1996

Fingerprint

Conformations
Molecular orbitals
Benzene
Magnetic properties
Polymers
Molecules
Geometry
nitroxyl

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Through-Bond and Through-Space Interactions of Organic Radicals Coupled by m-Phenylene. / Yoshizawa, Kazunari; Kuga, Takao; Sato, Tohru; Hatanaka, Masashi; Tanaka, Kazuyoshi; Yamabe, Tokio.

In: Bulletin of the Chemical Society of Japan, Vol. 69, No. 12, 12.1996, p. 3443-3450.

Research output: Contribution to journalArticle

Yoshizawa, Kazunari ; Kuga, Takao ; Sato, Tohru ; Hatanaka, Masashi ; Tanaka, Kazuyoshi ; Yamabe, Tokio. / Through-Bond and Through-Space Interactions of Organic Radicals Coupled by m-Phenylene. In: Bulletin of the Chemical Society of Japan. 1996 ; Vol. 69, No. 12. pp. 3443-3450.
@article{a7956d294c6447879c3a7ef218ec7a76,
title = "Through-Bond and Through-Space Interactions of Organic Radicals Coupled by m-Phenylene",
abstract = "Through-bond and through-space magnetic interactions in tricarbene and its related triradicals coupled through m-phenylene units are discussed with a semiempirical molecular orbital method including configuration interactions (PM3-CI method). The high-spin (HS) and low-spin (LS) states have quite similar geometries, but the methylene bridging angle is larger in the HS states. The HS states of these lie well below the corresponding LS states, except for one which contains nitroxide and aminiumyl radicals. Instability of the HS state of the heteroatomic system is a consequence of significant mixing between NBMOs and benzene elg-type orbitals, which can be explained in terms of simple perturbation theory. The energy difference between the HS and LS states is not explicitly influenced by the conformation of the molecules examined. This shows that such conformations have little effect on the magnetic properties in possible polymer ferromagnets which contain m-phenylene coupling units, as far as the second nearest neighbor interaction.",
author = "Kazunari Yoshizawa and Takao Kuga and Tohru Sato and Masashi Hatanaka and Kazuyoshi Tanaka and Tokio Yamabe",
year = "1996",
month = "12",
doi = "10.1246/bcsj.69.3443",
language = "English",
volume = "69",
pages = "3443--3450",
journal = "Bulletin of the Chemical Society of Japan",
issn = "0009-2673",
publisher = "The Chemical Society of Japan",
number = "12",

}

TY - JOUR

T1 - Through-Bond and Through-Space Interactions of Organic Radicals Coupled by m-Phenylene

AU - Yoshizawa, Kazunari

AU - Kuga, Takao

AU - Sato, Tohru

AU - Hatanaka, Masashi

AU - Tanaka, Kazuyoshi

AU - Yamabe, Tokio

PY - 1996/12

Y1 - 1996/12

N2 - Through-bond and through-space magnetic interactions in tricarbene and its related triradicals coupled through m-phenylene units are discussed with a semiempirical molecular orbital method including configuration interactions (PM3-CI method). The high-spin (HS) and low-spin (LS) states have quite similar geometries, but the methylene bridging angle is larger in the HS states. The HS states of these lie well below the corresponding LS states, except for one which contains nitroxide and aminiumyl radicals. Instability of the HS state of the heteroatomic system is a consequence of significant mixing between NBMOs and benzene elg-type orbitals, which can be explained in terms of simple perturbation theory. The energy difference between the HS and LS states is not explicitly influenced by the conformation of the molecules examined. This shows that such conformations have little effect on the magnetic properties in possible polymer ferromagnets which contain m-phenylene coupling units, as far as the second nearest neighbor interaction.

AB - Through-bond and through-space magnetic interactions in tricarbene and its related triradicals coupled through m-phenylene units are discussed with a semiempirical molecular orbital method including configuration interactions (PM3-CI method). The high-spin (HS) and low-spin (LS) states have quite similar geometries, but the methylene bridging angle is larger in the HS states. The HS states of these lie well below the corresponding LS states, except for one which contains nitroxide and aminiumyl radicals. Instability of the HS state of the heteroatomic system is a consequence of significant mixing between NBMOs and benzene elg-type orbitals, which can be explained in terms of simple perturbation theory. The energy difference between the HS and LS states is not explicitly influenced by the conformation of the molecules examined. This shows that such conformations have little effect on the magnetic properties in possible polymer ferromagnets which contain m-phenylene coupling units, as far as the second nearest neighbor interaction.

UR - http://www.scopus.com/inward/record.url?scp=0006918228&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0006918228&partnerID=8YFLogxK

U2 - 10.1246/bcsj.69.3443

DO - 10.1246/bcsj.69.3443

M3 - Article

AN - SCOPUS:0006918228

VL - 69

SP - 3443

EP - 3450

JO - Bulletin of the Chemical Society of Japan

JF - Bulletin of the Chemical Society of Japan

SN - 0009-2673

IS - 12

ER -