Abstract
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)...Continue Reading
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