Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles
Dicopper(II,II) and dicopper(I,II) complexes of a series of dinucleating macrocycles
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一系列双核大环化合物的二铜(II,II)和二铜(I,II)配合物
DOI：
10.1039/dt9930000253
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发表时间：
1993
期刊：
影响因子：
--
通讯作者：
D. Fenton
中科院分区：
文献类型：
--
作者：
H. Ōkawa;M. Tadokoro;Yūichiro Aratake;M. Ohba;K. Shindo;M. Mitsumi;Masayuki Koikawa;Mie Tomono;D. Fenton
在（2,3）、（2,4）、（2,5）、（3,3）、（3,4）、（2,5）、（3,3）、（3,4）胺氮上，通过（CH2）m和（CH2）n两条烷烃链结合了两个2,6-二（氨基甲基）-4-甲基苯酚二核大环H2Lm，n。制备了通式为[Cu2Lm，n][ClO4]2的双核铜（II）配合物。低温磁学研究（80-300 K）揭示了每个配合物内铜（II）离子之间的强反铁磁自旋交换（J基于h = -2JS1S2，范围在-345 ~ -255 cm-1）。循环伏安图显示两个还原对，cuicuii - cuicuii和CuICuII-CuICuI。用电化学方法测定了杂价CuICuII配合物的比例常数Kcom。Kcom值的增大顺序为（L2,3）2 - < (L2,4)2 - < (L2,5)2 -和（L3,3）2 - < (L3,4)2 -。根据ESR谱，所有配合物的CuICuII混合价态均为“自旋俘获态”（I类）。
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.