Construction of three high-nuclearity heterometallic cluster organic frameworks by introducing a bifunctional tripodal alcohol ligand

利用双功能三元醇配体构建3种高核数杂金属团簇有机骨架

Three new metal organic frameworks,[Mn^(Ⅲ)_(4)Mn^(Ⅱ)_(8)O_(2)(4-thmpy)_(4)(O_(2)CPh)_(10)(OMe)_(2)(H_(2)O)_(2)]·3CH_(3)OH·4H_(2)O(1),[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)O(4-thmpy)_(4)(O_(2)CPh)_(6)(H_(2)O)_(4)]·CH_(3)OH·3H_(2)O(2),and[Mn^(Ⅱ)_(4)Ni^(Ⅱ)_(6)O(4-thmpy)_(4)(O_(2)CPh)_(6)(H_(2)O)_(4)]·2CH_(3)OH·2H_(2)O(3),have been successfully synthesized by using 4-[tri-(hydroxymethyl)methyl]pyridine(4-thmpyH_(3))as ligand.Crystal structure analyses show that compound 1 is a disk-like twelve nuclear[Mn^(Ⅲ)_(4)Mn^(Ⅱ)_(8)]0D cluster.Compounds 2 and 3 are isomorphic,and the decanuclear heteronuclear cluster[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)]node in compound 2 can be seen as a hyper-tetrahedron of four coboundary cubic alkanes[Mn^(Ⅱ)Co^(Ⅱ)_(3)O_(4)],then each ten-nuclear heteronuclear cluster[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)]is connected by six 4-thmpy^(3-)with six adjacent decanuclear clusters[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)],forming the NaCl-type 3D topological structure.Magnetic studies showed that there exist antiferromagnetic interactions between metal ions in 1-3.

利用配体4-[三-(羟甲基)甲基]吡啶(4-thmpyH_(3)),成功合成了3种新型金属有机骨架[Mn^(Ⅲ)_(4)Mn^(Ⅱ)_(8)O_(2)(4-thmpy)_(4)(O_(2)CPh)_(10)(OMe)_(2)(H_(2)O)_(2)](1),[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)O(4-thmpy)_(4)(O_(2)CPh)_(6)(H_(2)O)_(4)](2)和[Mn^(Ⅱ)_(4)Ni^(Ⅱ)_(6)O(4-thmpy)_(4)(O_(2)CPh)_(6)(H_(2)O)_(4)](3)。晶体结构分析表明,化合物1表现为圆盘状十二核[Mn^(Ⅲ)_(4)Mn^(Ⅱ)_(8)]零维簇。化合物2和3是同构的。化合物2中的十核簇[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)]节点可以看作是4个共界立方烷[Mn^(Ⅱ)Co^(Ⅱ)_(3)O_(4)]组成的超四面体,每个十核簇[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)]通过6个4-thmpy^(3-)与相邻的6个十核簇[Mn^(Ⅱ)_(4)Co^(Ⅱ)_(6)]连接,形成NaCl型三维拓扑结构。磁性研究表明,化合物1-3金属离子之间存在反铁磁相互作用。