National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan.
Inorg Chem. 2009 Jul 6;48(13):5861-73. doi: 10.1021/ic900128t.
By introducing the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (L(1)) and 1,4-bis(imidazole-1-ylmethyl)benzene (L(2)) ligands into the molybdate system under hydrothermal conditions, 12 novel isopolymolybdate frameworks were obtained: [CuL(1)(H(2)O)][Mo(3)O(10)] (1), [ML(1)(H(2)O)(2)][Mo(3)O(10)] [M = Cu (2), Zn (3), and Co (4)], [Cu(2)(L(1))(4)][theta-Mo(8)O(26)] (5), [Cu(4)(L(1))(4)]beta-Mo(8)O(26)gamma-Mo(8)O(26).H(2)O (6), [Ag(4)(L(1))(2)][beta-Mo(8)O(26)] (7), [M(2)(L(1))(3)(H(2)O)(4)][beta-Mo(8)O(26)].2H(2)O [M = Zn (8), Co (9), and Ni (10)], and [M(4)(L(2))(4)][delta-Mo(8)O(26)] [M = Cu (11) and Ag (12)]. Compound 1 and isostructural compounds 2-4 exhibit similar three-dimensional (3D) pillar-layered structures. Compound 5 shows a novel pillar-layered framework constructed from two sorts of CuL(1) left- and right-handed helical chains and the theta-Mo(8)O(26) polyoxoanion. Compound 6 contains two sorts of isomers of beta-Mo(8)O(26) and gamma-Mo(8)O(26) coexisting in one structure, which induce the formation of two sorts of ladderlike building blocks and finally the polythread structure. The cationic and anionic fragments in compound 7, the dinuclear molecular loop of Ag(2)(L(1))(2) and beta-Mo(8)O(26), are both linked up by single Ag ions, forming two kinds of infinite chains of Ag(3)(L(1))(2)(3n+) and Ag-beta-Mo(8)O(26)(3n-), respectively. Compounds 8-10 are isostructural and exhibit the parallel two-fold (2D-->2D) interpenetrated networks based on the beta-Mo(8)O(26) cluster. Isostructural compounds 11 and 12 have 3D polythread penetrated frameworks based on the delta-Mo(8)O(26) polyoxoanion. The luminescent properties of the ligands and complexes 3, 6-8, and 11-12 are investigated in the solid state.
通过在水热条件下引入柔性的 1,4-双（1,2,4-三唑-1-基甲基）苯（L(1)）和 1,4-双（咪唑-1-基甲基）苯（L(2)）配体，得到了 12 个新型同多钼酸盐框架：[CuL(1)(H(2)O)][Mo(3)O(10)] (1)、[ML(1)(H(2)O)(2)][Mo(3)O(10)] [M = Cu (2)、Zn (3) 和 Co (4)]、[Cu(2)(L(1))(4)][theta-Mo(8)O(26)] (5)、[Cu(4)(L(1))(4)]beta-Mo(8)O(26)gamma-Mo(8)O(26).H(2)O (6)、[Ag(4)(L(1))(2)][beta-Mo(8)O(26)] (7)、[M(2)(L(1))(3)(H(2)O)(4)][beta-Mo(8)O(26)].2H(2)O [M = Zn (8)、Co (9) 和 Ni (10)] 和 [M(4)(L(2))(4)][delta-Mo(8)O(26)] [M = Cu (11) 和 Ag (12)]。化合物 1 和结构相似的化合物 2-4 表现出相似的三维（3D）支柱层状结构。化合物 5 展示了一种由两种类型的CuL(1)左、右手螺旋链和 theta-Mo(8)O(26)多氧阴离子构成的新型支柱层状骨架。化合物 6 含有两种类型的 beta-Mo(8)O(26)和 gamma-Mo(8)O(26)同构物共存于一个结构中，诱导形成两种类型的梯形构建块，最终形成多线程结构。化合物 7 中的阳离子和阴离子片段、Ag(2)(L(1))(2)和 beta-Mo(8)O(26)的双核分子环，均由单个 Ag 离子连接，形成了两种类型的无限链Ag(3)(L(1))(2)(3n+)和Ag-beta-Mo(8)O(26)(3n-)。化合物 8-10 结构相似，表现出基于 beta-Mo(8)O(26)簇的平行二倍体（2D-->2D）互穿网络。结构相似的化合物 11 和 12 具有基于 delta-Mo(8)O(26)多氧阴离子的 3D 多线程穿透骨架。研究了配体和配合物 3、6-8 和 11-12 的固态发光性质。
