Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)] +[TCNE].-

Shinji Mikami; Ken Ichi Sugiura; Tatsuo Maruta; Yonezo Maeda; Masaaki Ohba; Naoki Usuki; Hisashi Okawa; Tomoyuki Akutagawa; Sadafumi Nisihara; Takayoshi Nakamura; Kentaro Iwasaki; Nobuyuki Miyazaki; Shojun Hino; Eiji Asato; Joel S. Miller; Yoshiteru Sakata

doi:10.1039/b007931f

Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^III(TPP)] ⁺[TCNE]^.-

Shinji Mikami, Ken Ichi Sugiura, Tatsuo Maruta, Yonezo Maeda, Masaaki Ohba, Naoki Usuki, Hisashi Okawa, Tomoyuki Akutagawa, Sadafumi Nisihara, Takayoshi Nakamura, Kentaro Iwasaki, Nobuyuki Miyazaki, Shojun Hino, Eiji Asato, Joel S. Miller, Yoshiteru Sakata

Inorganic and Analytical Chemistry

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [Fe^II(TPP)], formed the electron transfer salt (ETS) [Fe^III(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [Fe^III(TPP)]⁺ and bridging μ-[TCNE]^.- with Fe-N^TCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from Fe^II to TCNE produces S = 1/2 [Fe^III(TPP)]⁺ having a (d_xy)²(d_yz,d_zx)³ configuration and S = 1/2 [TCNE]^.-. ⁵⁷Fe Mössbauer data, δ = 0.28 mm s^-1 and ΔE = 2.19 mm s^-1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μ_B, arises from two S = 1/2 systems having antiferromagnetic coupling, -190 cm^-1 (H = -2Σ J _ijS_iS_j).

Original language	English
Pages (from-to)	448-455
Number of pages	8
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	4
DOIs	https://doi.org/10.1039/b007931f
Publication status	Published - 2001

All Science Journal Classification (ASJC) codes

Chemistry(all)

Access to Document

10.1039/b007931f

Cite this

Mikami, S., Sugiura, K. I., Maruta, T., Maeda, Y., Ohba, M., Usuki, N., Okawa, H., Akutagawa, T., Nisihara, S., Nakamura, T., Iwasaki, K., Miyazaki, N., Hino, S., Asato, E., Miller, J. S., & Sakata, Y. (2001). Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^III(TPP)] ⁺[TCNE]^.-. Journal of the Chemical Society, Dalton Transactions, (4), 448-455. https://doi.org/10.1039/b007931f

Mikami, S, Sugiura, KI, Maruta, T, Maeda, Y, Ohba, M, Usuki, N, Okawa, H, Akutagawa, T, Nisihara, S, Nakamura, T, Iwasaki, K, Miyazaki, N, Hino, S, Asato, E, Miller, JS & Sakata, Y 2001, 'Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^III(TPP)] ⁺[TCNE]^.-', Journal of the Chemical Society, Dalton Transactions, no. 4, pp. 448-455. https://doi.org/10.1039/b007931f

@article{1a568233cebb42f9b4a1a85e94702c59,

title = "Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)] +[TCNE].-",

abstract = "The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE].- with Fe-NTCNE distance 1.889(2) {\AA}. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE].-. 57Fe M{\"o}ssbauer data, δ = 0.28 mm s-1 and ΔE = 2.19 mm s-1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, -190 cm-1 (H = -2Σ J ijSiSj).",

author = "Shinji Mikami and Sugiura, {Ken Ichi} and Tatsuo Maruta and Yonezo Maeda and Masaaki Ohba and Naoki Usuki and Hisashi Okawa and Tomoyuki Akutagawa and Sadafumi Nisihara and Takayoshi Nakamura and Kentaro Iwasaki and Nobuyuki Miyazaki and Shojun Hino and Eiji Asato and Miller, {Joel S.} and Yoshiteru Sakata",

year = "2001",

doi = "10.1039/b007931f",

language = "English",

pages = "448--455",

journal = "Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "4",

}

TY - JOUR

T1 - Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [FeIII(TPP)] +[TCNE].-

AU - Mikami, Shinji

AU - Sugiura, Ken Ichi

AU - Maruta, Tatsuo

AU - Maeda, Yonezo

AU - Ohba, Masaaki

AU - Usuki, Naoki

AU - Okawa, Hisashi

AU - Akutagawa, Tomoyuki

AU - Nisihara, Sadafumi

AU - Nakamura, Takayoshi

AU - Iwasaki, Kentaro

AU - Miyazaki, Nobuyuki

AU - Hino, Shojun

AU - Asato, Eiji

AU - Miller, Joel S.

AU - Sakata, Yoshiteru

PY - 2001

Y1 - 2001

N2 - The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE].- with Fe-NTCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE].-. 57Fe Mössbauer data, δ = 0.28 mm s-1 and ΔE = 2.19 mm s-1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, -190 cm-1 (H = -2Σ J ijSiSj).

AB - The direct redox reaction between tetracyanoethylene (TCNE) and meso-tetraphenylporphyrinatoiron(II), [FeII(TPP)], formed the electron transfer salt (ETS) [FeIII(TPP)][TCNE], which has been structurally, spectroscopically, and magnetically characterized. It has an extended one-dimensional linear chain with coordination polymer motif comprised of [FeIII(TPP)]+ and bridging μ-[TCNE].- with Fe-NTCNE distance 1.889(2) Å. This coordination geometry is consistent with a low-spin iron(III) ion, i.e., one electron transfer from FeII to TCNE produces S = 1/2 [FeIII(TPP)]+ having a (dxy)2(dyz,dzx)3 configuration and S = 1/2 [TCNE].-. 57Fe Mössbauer data, δ = 0.28 mm s-1 and ΔE = 2.19 mm s-1 at 77 K, also support the low-spin state. The room temperature magnetic moment of the ETS, 1.20 μB, arises from two S = 1/2 systems having antiferromagnetic coupling, -190 cm-1 (H = -2Σ J ijSiSj).

UR - http://www.scopus.com/inward/record.url?scp=0035925340&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035925340&partnerID=8YFLogxK

U2 - 10.1039/b007931f

DO - 10.1039/b007931f

M3 - Article

AN - SCOPUS:0035925340

SN - 1470-479X

SP - 448

EP - 455

JO - Dalton Transactions

JF - Dalton Transactions

IS - 4

ER -

Structure, optical and magnetic behaviour of meso- tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^III(TPP)] ⁺[TCNE]^.-

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this