Framework control by a metalloligand having multicoordination ability: new synthetic approach for crystal structures and magnetic properties.
Framework control by a metalloligand having multicoordination ability: new synthetic approach for crystal structures and magnetic properties.
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DOI：
10.1021/ic049550e
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发表时间：
2005-01
影响因子：
4.6
通讯作者：
S. Noro;H. Miyasaka;S. Kitagawa;T. Wada;T. Okubo;M. Yamashita;T. Mitani
中科院分区：
文献类型：
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作者：
S. Noro;H. Miyasaka;S. Kitagawa;T. Wada;T. Okubo;M. Yamashita;T. Mitani
利用具有两种配位基团的新型金属配体L(Cu)，[Cu(2，4-pydca)(2)](2)(-)(2，4-pydca(2)(-)=吡啶-2，4-二羧酸)与一系列第一周期过渡金属离子(Mn(II)，Fe(II)，Co(II)，Cu(II)，Zn(II))选择性成键。根据4-羧酸盐与Co(II)、Cu(II)和Zn(II)离子的配位方式，L(Cu)形成了一维(1-d)的组装，其重复基序为[-M-O(2)C-(Py)N-Cu-N(Py)-Co(2)-]：{[ZnL(Cu)(H(2)O)(3)(DMF)].DMF}(N)()(2)，[ZnL(Cu)(H(2)O)(2)(MeOH)(2)](N)()(3)和{[ML(Cu)(H(2)O)(4)].2H(2)O}(N)()(M=Co(4)，Cu(5)，Zn(6))。使用2，2‘-联吡啶(2，2’-bpy)的末端配体，再加上铜(II)离子，得到了一个锯齿形的一维组装，其重复单元类似于4-6：{[Cu(2，2‘-bpy)L(铜)].3H(2)O}(N)()(9)。另一方面，对于Mn(II)和Fe(II)离子，L(铜)以2-羧酸桥联的方式形成另一个具有重复基元[-M-O-C-O-Cu-O-C-O-]：[ML(Cu)(H(2)O)(4)](N)()(M=Mn(7)，Fe(8))的一维组装。这种选择性与路易斯碱度的强弱以及L(铜)和欧文-威廉斯级数对金属离子的静电效应有关。根据它们的桥联模式，得到了不同的磁性：磁心之间具有4-羧基吡啶酸桥的4，5和9具有弱的反铁磁相互作用，而磁心之间具有羧酸桥的7和8表现出一维铁磁行为(对于7，M(II)=Mn(II)，J/k(B)=0.69K；对于8，M(II)=Fe(II)，J/k(B)=0.71 K)。
By utilizing the novel metalloligand l(Cu), [Cu(2,4-pydca)(2)](2)(-) (2,4-pydca(2)(-) = pyridine-2,4-dicarboxylate), which possesses two kinds of coordination groups, selective bond formation with the series of the first-period transition metal ions (Mn(ii), Fe(ii), Co(ii), Cu(ii), and Zn(ii)) has been accomplished. depending on the coordination mode of 4-carboxylate with Co(ii), Cu(ii), and Zn(ii) ions, L(Cu) forms a one-dimensional (1-d) assembly with a repeating motif of [-M-O(2)C-(py)N-Cu-N(py)-Co(2)-]: {[ZnL(Cu)(H(2)O)(3)(DMF)].DMF}(N)() (2), [ZnL(Cu)(H(2)O)(2)(MeOH)(2)](N)() (3), and {[ML(Cu)(H(2)O)(4)].2H(2)O}(N)() (M = Co (4), Cu (5), Zn (6)). the use of a terminal ligand of 2,2'-bipyridine (2,2'-bpy), in addition to the cu(ii) ion, gives a zigzag 1-d assembly with the similar repeating unit as 4-6: {[Cu(2,2'-bpy)L(Cu)].3H(2)O}(N)() (9). on the other hand, for Mn(ii) and Fe(ii) ions, L(Cu) shows a 2-carboxylate bridging mode to form an another 1-d assembly with a repeating motif of [-M-O-C-O-CU-O-C-O-]: [ML(Cu)(H(2)O)(4)](N)() (M = Mn (7), Fe (8)). this selectivity is related to the strength of lewis basicity and the electrostatic effect of L(Cu) and the irving-williams order on the present metal ions. according to their bridging modes, a variety of magnetic properties are obtained: 4, 5, and 9, which have the 4-carboxypyridinate bridge between magnetic centers, have weak antiferromagnetic interaction, whereas 7 and 8 with the carboxylate bridge between magnetic centers reveal 1-d ferromagnetic behavior (Cu(II)-M(II); M(II) = Mn(II), J/k(B) = 0.69 K for 7; M(II) = Fe(II), J/k(B) = 0.71 K for 8).