Wu Jing-Yun, Zhong Ming-Shiou, Chiang Ming-Hsi
Department of Applied Chemistry, National Chi Nan University, Nantou, 545, Taiwan.
Institute of Chemistry, Academia Sinica, Taipei, 115, Taiwan.
Chemistry. 2017 Nov 13;23(63):15957-15965. doi: 10.1002/chem.201702848. Epub 2017 Oct 17.
Self-assembly of Cu(NO ) ⋅3 H O and di(3-pyridylmethyl)amine (dpma) with addition of different acids (HNO , HOAc, HCl, HClO , HOTf, HPF , HBF , and H SO ) afforded a family of anion-templated tetragonal metallocages with a cationic prismatic structure of [(G )⊂{Cu (Hdpma) }] (G =NO , PF , SiF ) with different ligating anions/solvents (NO , Cl , ClO , OTf , H O) outside the cage. Systematic competitive experiments have rationalized the tendency of anion templation towards the formation of metallocages [(G )⊂{Cu (Hdpma) }] as occurring in the order SiF ≈PF >NO >SO ≈ClO ≈BF . This sequence is mostly elucidated by shape control over size selectivity and electrostatic attraction between the cationic {Cu (Hdpma) } host and the anionic guests. In addition, these results have also roughly ranked the anion coordination ability in the order Cl , ClO , OTf >NO >BF , CH SO . Magnetic studies of metallocages 1 t and 2-4 suggest that the fitted magnetic interaction, being weakly magnetically coupled overall, is interpreted as a result of the combination of intracage ferromagnetic coupling integrals and intercage antiferromagnetic exchange; both contributions are very weak and comparable in strength.
将硝酸铜三水合物（Cu(NO₃)₂·3H₂O）与二（3 - 吡啶甲基）胺（dpma）加入不同的酸（HNO₃、HOAc、HCl、HClO₄、HOTf、HPF₆、HBF₄和H₂SO₄）进行自组装，得到了一系列阴离子模板化的四方金属笼，其具有阳离子棱柱结构[(Gₓ)⊂{Cu₄(Hdpma)₆}]（Gₓ = NO₃⁻、PF₆⁻、SiF₆²⁻），在笼外具有不同的配位阴离子/溶剂（NO₃⁻、Cl⁻、ClO₄⁻、OTf⁻、H₂O）。系统的竞争实验已经阐明了阴离子模板化形成金属笼[(Gₓ)⊂{Cu₄(Hdpma)₆}]的倾向，其顺序为SiF₆²⁻≈PF₆⁻>NO₃⁻>SO₄²⁻≈ClO₄⁻≈BF₄⁻。这个顺序主要是通过阳离子{Cu₄(Hdpma)₆}主体与阴离子客体之间的尺寸选择性形状控制和静电吸引来解释的。此外，这些结果还大致将阴离子配位能力按Cl⁻、ClO₄⁻、OTf⁻>NO₃⁻>BF₄⁻、CH₃SO₃⁻的顺序排列。对金属笼1 - t和2 - 4的磁性研究表明，拟合的磁相互作用总体上是弱磁耦合的，这被解释为笼内铁磁耦合积分和笼间反铁磁交换相结合的结果；这两种贡献都非常弱且强度相当。
