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

研究成果: ジャーナルへの寄稿学術誌査読

79 被引用数 (Scopus)


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.

ジャーナルJournal of the Chemical Society, Dalton Transactions
出版ステータス出版済み - 1993

!!!All Science Journal Classification (ASJC) codes

  • 化学一般


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