Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties
Auxiliary ligand-induced structural diversities of octacyanometalate-based heterobimetallic coordination polymers towards diverse magnetic properties
复制标题
辅助配体诱导的八氰基金属盐基异双金属配位聚合物的结构多样性，以实现不同的磁性能
DOI：
10.1039/c9dt00654k
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发表时间：
2019-06-14
影响因子：
4
通讯作者：
Zhang, Chi
中科院分区：
文献类型：
--
作者：
Qian, Jun;Yoshikawa, Hirofumi;Zhang, Chi
合成了三种基于八氰尿酸盐的双金属配位聚合物{[mu（4）-MV（CN）8][Co（DMF）（4）]（2）（ClO 4）}（n）（M = W CP-1，Mo CP-2）和{[mu（4）-W-IV（CN）（8）]Co-2（azpy）（4）}（n）CP-3，在无（对于CP 1和2）或存在（对于CP-3）辅助配体4，4 '-偶氮吡啶（azpy）。CP 1和2显示出相同的三维（3D）聚合阳离子骨架，[ClO 4]（-）作为抗衡离子，而CP-3显示出不寻常的2-节点（4，6）-连接的4，6 T155拓扑结构的多孔3D骨架，其点符号为{4（2）中心点6（4）}{4（6）中心点6（4）中心点7中心点8（4）}（2）。值得注意的是，在CP-3的合成过程中，八氰尿酸盐[W-V（CN）（8）]（3-）被还原成[W-IV（CN）（8）]（4-）。磁性研究表明，CP-1表现出典型的铁磁性质，这是由于W（V）和Co（II）自旋中心之间的铁磁耦合，而CP-3在低温下表现出弱的铁磁相互作用，这与CP-3中W中心的价态变化一致.
Three octacyanometalate-based bimetallic coordination polymers (CPs), {[mu(4)-MV(CN) 8][Co(DMF)(4)](2)(ClO4)}(n) (M = W CP-1, Mo CP-2) and {[mu(4)-W-IV(CN)(8)]Co-2(azpy)(4)}(n) CP-3, were synthesized in the absence (for CPs 1 and 2) or presence (for CP-3) of auxiliary ligand 4,4'-azopyridine (azpy), respectively. CPs 1 and 2 exhibit the same three-dimensional (3D) polymeric cation frameworks with [ClO4](-) as the counterions, while CP-3 displays a porous 3D framework in an unusual 2-nodal (4,6)-connected 4,6T155 topology with point symbol as {4(2)center dot 6(4)}{4(6)center dot 6(4)center dot 7 center dot 8(4)}(2). Notably is that octacyanometalate [W-V(CN)(8)](3-) has been reduced into [W-IV(CN)(8)](4-) during the synthetic process of CP-3. The magnetic investigations indicate that CP-1 exhibits the typical ferromagnetic property due to the ferromagnetic coupling between W(V) and Co(II) spin centers, while CP-3 displays the weak ferromagnetic interaction at low temperature, which is consistent with the valence change of W center in CP-3.