An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)

Miki Nishi; Ryuta Ishii; Mitsuo Ikeda; Noriaki Hanasaki; Norihisa Hoshino; Tomoyuki Akutagawa; Michinori Sumimoto; Masaki Matsuda

doi:10.1039/c7dt04649a

An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)

Miki Nishi, Ryuta Ishii, Mitsuo Ikeda, Noriaki Hanasaki, Norihisa Hoshino, Tomoyuki Akutagawa, Michinori Sumimoto, Masaki Matsuda

研究成果: Article › 査読

4 被引用数 (Scopus)

抄録

A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[Fe^III(tbp)Br₂]₂ (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br₂]₂ was isostructural to the reported TPP[Fe(Mc)L₂]₂ systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br₂] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br₂]₂ and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br₂]₂ was expected to be smaller than that for TPP[Fe(tbp)(CN)₂]₂. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.

本文言語	English
ページ（範囲）	4070-4075
ページ数	6
ジャーナル	Dalton Transactions
巻	47
号	12
DOI	https://doi.org/10.1039/c7dt04649a
出版ステータス	Published - 2018

ASJC Scopus subject areas

無機化学

文献へのアクセス

10.1039/c7dt04649a

他のファイルとリンク

引用スタイル

@article{4019ea92f61048c585b7cfc69ad356ee,

title = "An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)",

abstract = "A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.",

author = "Miki Nishi and Ryuta Ishii and Mitsuo Ikeda and Noriaki Hanasaki and Norihisa Hoshino and Tomoyuki Akutagawa and Michinori Sumimoto and Masaki Matsuda",

note = "Funding Information: This study was supported in part by a Grant-in-Aid for Scientific Research (C) (No. 16K05752) and a Grant-in-Aid for JSPS Research Fellow (No. 16J00164) from the Japan Society for the Promotion of Science. Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c7dt04649a",

language = "English",

volume = "47",

pages = "4070--4075",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "12",

}

TY - JOUR

T1 - An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)

AU - Nishi, Miki

AU - Ishii, Ryuta

AU - Ikeda, Mitsuo

AU - Hanasaki, Noriaki

AU - Hoshino, Norihisa

AU - Akutagawa, Tomoyuki

AU - Sumimoto, Michinori

AU - Matsuda, Masaki

N1 - Funding Information: This study was supported in part by a Grant-in-Aid for Scientific Research (C) (No. 16K05752) and a Grant-in-Aid for JSPS Research Fellow (No. 16J00164) from the Japan Society for the Promotion of Science. Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018

Y1 - 2018

N2 - A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.

AB - A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.

UR - http://www.scopus.com/inward/record.url?scp=85044240766&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85044240766&partnerID=8YFLogxK

U2 - 10.1039/c7dt04649a

DO - 10.1039/c7dt04649a

M3 - Article

C2 - 29417967

AN - SCOPUS:85044240766

SN - 1477-9226

VL - 47

SP - 4070

EP - 4075

JO - Dalton Transactions

JF - Dalton Transactions

IS - 12

ER -

An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)

抄録

ASJC Scopus subject areas

文献へのアクセス

他のファイルとリンク

フィンガープリント

引用スタイル