Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. a series of novel polyoxotungstates sandwiched by octa-copper clusters.
The reaction of CuCl(2).2 H2O with trivacant Keggin polyoxoanions K8Na2[A-alpha-GeW9O34].25 H2O or K10[A-alpha-SiW9O34].25 H2O in the presence of 1,2-diaminopropane (dap), ethylenediamine (en) or 2,2'-bipyridine (2,2'-bpy) under hydrothermal conditions afforded five novel hybrid inorganic-organic octa-Cu sandwiched polyoxotungstates (POTs): H4[CuII8(dap)4(H2O)2(B-alpha-GeW9O34)2].13 H2O (1), (H2en)2[CuII8-(en)4(H2O)2(B-alpha-GeW9O34)2].5 H2O(2), (H2en)2[CuII8(en)4(H2O)2(B-alpha-SiW9-O34)2].8 H2O (3), [CuII(H2O)2]H2[CuII8-(en)4(H2O)2(B-alpha-SiW9O34)2] (4), and [CuII2(H2O)2(2,2'-bpy)2]{[CuII(bdyl)]2-[CuII8(2,2'-bpy)4(H2O)2(B-alpha-GeW9-O34)2]}.4 H2O (bdyl=2,2'-bipyridinyl)(5). Additionally, CuCl(2).2 H2O reacts with the mixture of GeO2, Na2WO(4).2 H2O, H2SiW12O(40).2 H2O in the presence of 2,2'-bpy and 4,4'-bpy under hydrothermal conditions leading to another novel mixed-valent octa-Cu sandwiched POT hybrid: [CuI(2,2'-bpy)(4,4'-bpy)]2[{CuI2(2,2'-bpy)2(4,4'-bpy)]2[CuI2CuII6(2,2'-bpy)2(4,4'-bpy)2(B-alpha-GeW9O34)2}].2 H2O (6). 1, 2, and 3 are discrete dimers constructed from two trivacant Keggin [B-alpha-XW9O34]10- (X=GeIV/SiIV) fragments and an octa-Cu cluster whereas 4 displays the 3D (3,6)-connected nets with (4.6(2))(4(2).6(4).8(7).10(2)) topology, which are built by octa-Cu sandwiched polyoxometalate building blocks through copper cation bridges. 5 is a novel 2D layer based on octa-Cu sandwiched POT clusters and [CuII2(bdyl)] units. Interestingly, the rollover metalation of 2,2'-bpy is firstly observed in the system containing the copper complex under hydrothermal conditions. 6 is a discrete mixed-valent octa-Cu sandwiched POT supported by two CuI-complexes [CuI2-(2,2'-bpy)2(4,4'-bpy)]2+ through 4,4'-bpy bridges, which constructs a novel dodeca-copper cluster. Notably, the octa-Cu cluster in 6 is mixed-valent and is different from those in 1-5. To our knowledge, 1-6 represent a rare family of POTs incorporating novel octa-nuclear transition-metal clusters in polyoxometalate chemistry. They were structurally characterized by FT-IR spectra, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. The magnetic properties of 1, 4, and 5 were quantitatively analyzed by the MAGPACK software package.
Zhao
Jun-Wei
JW
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter and Graduate School of the Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Wang
Chun-Mei
CM
Zhang
Jie
J
Zheng
Shou-Tian
ST
Yang
Guo-Yu
GY