Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.
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DOI:
10.1002/anie.201600694
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发表时间:
2016-04-25
影响因子:
16.6
通讯作者:
Layfield, Richard A.
Layfield, Richard A.
中科院分区:
化学1区
文献类型:
--
作者:
Moilanen, Jani O.;Chilton, Nicholas F.;Day, Benjamin M.;Pugh, Thomas;Layfield, Richard A.

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在18-c-6存在下,用钾还原六氮杂杂萘(HAN)生成[{K(18-c-6)}HAN],其中含有S=1/2自由基[HAN].−。[HAN].−自由基可以转移到钴(II)酰胺[Co{N(SiMe3)2}2]上,形成[K(18-c-6)][(HAN){Co(N‘)2}3],磁性测量表明该化合物是一个S=4自旋体系,具有很强的钴配体反铁磁交换和J≈−2 90 cm−1(−2 J形式)。相反,未还原类似物[(HAN){Co(N‘’)2}3]中的CoII中心是弱耦合的(J≈−4.4 cm−1)。[HAN].−可以作为稳定的盐合成并转移到钴上,这一发现为基于强耦合的三角形HAN构建块的磁性材料提供了潜在的新途径。
Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18‐c‐6 produces [{K(18‐c‐6)}HAN], which contains the S=1/2 radical [HAN].−. The [HAN].− radical can be transferred to the cobalt(II) amide [Co{N(SiMe3)2}2], forming [K(18‐c‐6)][(HAN){Co(N′′)2}3]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt–ligand antiferromagnetic exchange and J≈−290 cm−1 (−2 J formalism). In contrast, the CoII centres in the unreduced analogue [(HAN){Co(N′′)2}3] are weakly coupled (J≈−4.4 cm−1). The finding that [HAN].− can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.
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