Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles

Hisashi Okawa, Makoto Tadokoro, Yuichiro Aratake, Masaaki Ohba, Kenji Shindo, Minoru Mitsumi, Masayuki Koikawa, Mie Tomono, David E. Fenton

Research output: Contribution to journalArticle

84 Citations (Scopus)

Abstract

The dinucleating macrocycles H2Lm,n containing two 2,6-di(aminomethyl)-4-methylphenol entities combined through two alkane chains, (CH2)m and (CH2)n, at the amine nitrogens have been prepared for the (m,n) sets (2,3), (2,4), (2,5), (3,3) and (3,4). The dinuclear copper(II) complexes having general formula [Cu2Lm,n][ClO4]2 have been prepared. Cryomagnetic investigations (80-300 K) reveal a strong antiferromagnetic spin-exchange between the copper(II) ions within each complex (J based on ℋ = -2JS1S2 in the range -345 to -255 cm-1). The cyclic voltammograms show two reduction couples, CuIICuII-CuICuII and CuICuII-CuICuI. The comproportionation constants Kcom for the mixed-valence CuICuII complexes have been determined electrochemically. The Kcom value increase in the order of the macrocycles (L2,3)2- < (L2,4)2- < (L2,5)2- and (L3,3)2- < (L3,4)2-. The CuICuII mixed-valence state is shown to be 'spin-trapped' (Class I) for all the complexes based on ESR spectra.

Original languageEnglish
Pages (from-to)253-258
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number2
DOIs
Publication statusPublished - 1993

Fingerprint

Copper
Alkanes
Amines
Paramagnetic resonance
Nitrogen
Ions
perchlorate
4-cresol

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles. / Okawa, Hisashi; Tadokoro, Makoto; Aratake, Yuichiro; Ohba, Masaaki; Shindo, Kenji; Mitsumi, Minoru; Koikawa, Masayuki; Tomono, Mie; Fenton, David E.

In: Journal of the Chemical Society, Dalton Transactions, No. 2, 1993, p. 253-258.

Research output: Contribution to journalArticle

Okawa, H, Tadokoro, M, Aratake, Y, Ohba, M, Shindo, K, Mitsumi, M, Koikawa, M, Tomono, M & Fenton, DE 1993, 'Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles', Journal of the Chemical Society, Dalton Transactions, no. 2, pp. 253-258. https://doi.org/10.1039/DT9930000253
Okawa, Hisashi ; Tadokoro, Makoto ; Aratake, Yuichiro ; Ohba, Masaaki ; Shindo, Kenji ; Mitsumi, Minoru ; Koikawa, Masayuki ; Tomono, Mie ; Fenton, David E. / Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles. In: Journal of the Chemical Society, Dalton Transactions. 1993 ; No. 2. pp. 253-258.
@article{1ef0f6507ef645228ad445fa687af71a,
title = "Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles",
abstract = "The dinucleating macrocycles H2Lm,n containing two 2,6-di(aminomethyl)-4-methylphenol entities combined through two alkane chains, (CH2)m and (CH2)n, at the amine nitrogens have been prepared for the (m,n) sets (2,3), (2,4), (2,5), (3,3) and (3,4). The dinuclear copper(II) complexes having general formula [Cu2Lm,n][ClO4]2 have been prepared. Cryomagnetic investigations (80-300 K) reveal a strong antiferromagnetic spin-exchange between the copper(II) ions within each complex (J based on ℋ = -2JS1S2 in the range -345 to -255 cm-1). The cyclic voltammograms show two reduction couples, CuIICuII-CuICuII and CuICuII-CuICuI. The comproportionation constants Kcom for the mixed-valence CuICuII complexes have been determined electrochemically. The Kcom value increase in the order of the macrocycles (L2,3)2- < (L2,4)2- < (L2,5)2- and (L3,3)2- < (L3,4)2-. The CuICuII mixed-valence state is shown to be 'spin-trapped' (Class I) for all the complexes based on ESR spectra.",
author = "Hisashi Okawa and Makoto Tadokoro and Yuichiro Aratake and Masaaki Ohba and Kenji Shindo and Minoru Mitsumi and Masayuki Koikawa and Mie Tomono and Fenton, {David E.}",
year = "1993",
doi = "10.1039/DT9930000253",
language = "English",
pages = "253--258",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1470-479X",
publisher = "Royal Society of Chemistry",
number = "2",

}

TY - JOUR

T1 - Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles

AU - Okawa, Hisashi

AU - Tadokoro, Makoto

AU - Aratake, Yuichiro

AU - Ohba, Masaaki

AU - Shindo, Kenji

AU - Mitsumi, Minoru

AU - Koikawa, Masayuki

AU - Tomono, Mie

AU - Fenton, David E.

PY - 1993

Y1 - 1993

N2 - The dinucleating macrocycles H2Lm,n containing two 2,6-di(aminomethyl)-4-methylphenol entities combined through two alkane chains, (CH2)m and (CH2)n, at the amine nitrogens have been prepared for the (m,n) sets (2,3), (2,4), (2,5), (3,3) and (3,4). The dinuclear copper(II) complexes having general formula [Cu2Lm,n][ClO4]2 have been prepared. Cryomagnetic investigations (80-300 K) reveal a strong antiferromagnetic spin-exchange between the copper(II) ions within each complex (J based on ℋ = -2JS1S2 in the range -345 to -255 cm-1). The cyclic voltammograms show two reduction couples, CuIICuII-CuICuII and CuICuII-CuICuI. The comproportionation constants Kcom for the mixed-valence CuICuII complexes have been determined electrochemically. The Kcom value increase in the order of the macrocycles (L2,3)2- < (L2,4)2- < (L2,5)2- and (L3,3)2- < (L3,4)2-. The CuICuII mixed-valence state is shown to be 'spin-trapped' (Class I) for all the complexes based on ESR spectra.

AB - The dinucleating macrocycles H2Lm,n containing two 2,6-di(aminomethyl)-4-methylphenol entities combined through two alkane chains, (CH2)m and (CH2)n, at the amine nitrogens have been prepared for the (m,n) sets (2,3), (2,4), (2,5), (3,3) and (3,4). The dinuclear copper(II) complexes having general formula [Cu2Lm,n][ClO4]2 have been prepared. Cryomagnetic investigations (80-300 K) reveal a strong antiferromagnetic spin-exchange between the copper(II) ions within each complex (J based on ℋ = -2JS1S2 in the range -345 to -255 cm-1). The cyclic voltammograms show two reduction couples, CuIICuII-CuICuII and CuICuII-CuICuI. The comproportionation constants Kcom for the mixed-valence CuICuII complexes have been determined electrochemically. The Kcom value increase in the order of the macrocycles (L2,3)2- < (L2,4)2- < (L2,5)2- and (L3,3)2- < (L3,4)2-. The CuICuII mixed-valence state is shown to be 'spin-trapped' (Class I) for all the complexes based on ESR spectra.

UR - http://www.scopus.com/inward/record.url?scp=37049066812&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37049066812&partnerID=8YFLogxK

U2 - 10.1039/DT9930000253

DO - 10.1039/DT9930000253

M3 - Article

SP - 253

EP - 258

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1470-479X

IS - 2

ER -