Atanasov Mihail, Comba Peter, Lampeka Yaroslaw D, Linti Gerald, Malcherek Thomas, Miletich Ronald, Prikhod'ko Alexander I, Pritzkow Hans
Universität Heidelberg, Anorganisch-Chemisches Institut, Germany.
Chemistry. 2006 Jan 11;12(3):737-48. doi: 10.1002/chem.200500365.
The reaction of M(CN)(6) (M = Cr(3+), Mn(3+), Fe(3+), Co(3+)) and M(CN)(8) (M = Mo(4+/5+), W(4+/5+)) with the trinuclear copper(II) complex of 1,3,5-triazine-2,4,6-triyltris[3-(1,3,5,8,12-pentaazacyclotetradecane)] (Cu(3)(L)) leads to partially encapsulated cyanometalates. With hexacyanometalate(III) complexes, Cu(3)(L) forms the isostructural host-guest complexes [[[Cu(3)(L)(OH(2))(2)]M(CN)(6)][M(CN)(6)]][M(CN)(6)]30 H(2)O with one bridging, two partially encapsulated, and one isolated M(CN)(6) unit. The octacyanometalates of Mo(4+/5+) and W(4+/5+) are encapsulated by two tris-macrocyclic host units. Due to the stability of the +IV oxidation state of Mo and W, only assemblies with M(CN)(8) were obtained. The Mo(4+) and W(4+) complexes were crystallized in two different structural forms: Cu(3)(L)(OH(2))[Mo(CN)(8)](8)15 H(2)O with a structural motif that involves isolated spherical Cu(3)(L)(OH(2))[M(CN)(8)] ions and a "string-of-pearls" type of structure [[Cu(3)(L)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O, with M(CN)(8) ions that bridge the encapsulated octacyanometalates in a two-dimensional network. The magnetic exchange coupling between the various paramagnetic centers is characterized by temperature-dependent magnetic susceptibility and field-dependent magnetization data. Exchange between the CuCu pairs in the Cu(3)(L) "ligand" is weakly antiferromagnetic. Ferromagnetic interactions are observed in the cyanometalate assemblies with Cr(3+), exchange coupling of Mn(3+) and Fe(3+) is very small, and the octacoordinate Mo(4+) and W(4+) systems have a closed-shell ground state.
M(CN)(6)（M = Cr(3+)、Mn(3+)、Fe(3+)、Co(3+)）和M(CN)(8)（M = Mo(4+/5+)、W(4+/5+)）与1,3,5-三嗪-2,4,6-三基三[3-(1,3,5,8,12-五氮杂环十四烷)]的三核铜(II)配合物（Cu(3)(L)）反应生成部分包封的氰基金属酸盐。与六氰基金属酸盐(III)配合物反应时，Cu(3)(L)形成同构的主客体配合物[[[Cu(3)(L)(OH(2))(2)]M(CN)(6)][M(CN)(6)]][M(CN)(6)]30 H(2)O，其中有一个桥连的、两个部分包封的和一个孤立的M(CN)(6)单元。Mo(4+/5+)和W(4+/5+)的八氰基金属酸盐被两个三大环主体单元包封。由于Mo和W的+IV氧化态的稳定性，仅得到了与M(CN)(8)形成的组装体。Mo(4+)和W(4+)配合物以两种不同的结构形式结晶：Cu(3)(L)(OH(2))[Mo(CN)(8)](8)15 H(2)O，其结构基序涉及孤立的球形Cu(3)(L)(OH(2))[M(CN)(8)]离子，以及一种“珍珠链”型结构[[Cu(3)(L)[M(CN)(8)]][M(CN)(8)]](NO(3))(4) 20 H(2)O，其中M(CN)(8)离子在二维网络中桥连被包封的八氰基金属酸盐。各种顺磁中心之间的磁交换耦合通过温度依赖的磁化率和场依赖的磁化数据来表征。Cu(3)(L)“配体”中CuCu对之间的交换是弱反铁磁性的。在与Cr(3+)形成的氰基金属酸盐组装体中观察到铁磁相互作用，Mn(3+)和Fe(3+)的交换耦合非常小，并且八配位的Mo(4+)和W(4+)体系具有闭壳基态。
