TY - JOUR
T1 - Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions
T2 - IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters
AU - Zhao, Jun Wei
AU - Wang, Chun Mei
AU - Zhang, Jie
AU - Zheng, Shou Tian
AU - Yang, Guo Yu
PY - 2008/10/20
Y1 - 2008/10/20
N2 - The reaction of CuCl2·2H2O with trivacant Keggin polyoxoanions K8Na2[A-α-GeW9O 34]·25H2O or K10[A-α-SiW 9O34]·25H2O 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): H 4[Cu8II(dap)4(H2O) 2(B-α-Ge-W9O34)2] ·13H2O (1), (H2en)2[Cu8 II-(en)4(H2O)2(B-α-GeW 9O34)2]·5H2O(2), (H 2en)2[Cu8II(en)4(H 2O)2(B-α-SiW9-O34) 2]·8H2O (3), [CuII(H2O) 2]H2:[Cu8II-(en)4(H 2O)2(B-α-SiW9O34) 2] (4), and [Cu2II(H2O) 2(2,2′-bpy)2]{[CuII(bdyl)] 2-[Cu8II(2,2′-bpy)4(H 2O)2(B-α-GeW9-O34) 2]}·4H2O (bdyl = 2,2′-bipyridinyl)(5). Additionally, CuCl2·2H2O reacts with the mixture of GeO2, Na2WO4·2H2O, H 2SiW12O40·2H2O 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: [Cu I(2,2′-bpy)(4,4′-bpy)]2[Cu2 I(2,2′-bpy)2(4,4′-bpy)]2[Cu 2ICu6I(2,2′-bpy) 2(4,4′-bpy)2(B-α-GeW9O 34)2)]·2H2O (6). 1, 2, and 3 are discrete dimers constructed from two trivacant Keggin [B-α-XW 9O34]10- (X = GeIV/SiIV) fragments and an octa-Cu cluster whereas 4 displays the 3D (3,6)-connected nets with (4·62)-(42·64·8 7·102) 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 [Cu 2II(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 [Cu2 I-(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.
AB - The reaction of CuCl2·2H2O with trivacant Keggin polyoxoanions K8Na2[A-α-GeW9O 34]·25H2O or K10[A-α-SiW 9O34]·25H2O 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): H 4[Cu8II(dap)4(H2O) 2(B-α-Ge-W9O34)2] ·13H2O (1), (H2en)2[Cu8 II-(en)4(H2O)2(B-α-GeW 9O34)2]·5H2O(2), (H 2en)2[Cu8II(en)4(H 2O)2(B-α-SiW9-O34) 2]·8H2O (3), [CuII(H2O) 2]H2:[Cu8II-(en)4(H 2O)2(B-α-SiW9O34) 2] (4), and [Cu2II(H2O) 2(2,2′-bpy)2]{[CuII(bdyl)] 2-[Cu8II(2,2′-bpy)4(H 2O)2(B-α-GeW9-O34) 2]}·4H2O (bdyl = 2,2′-bipyridinyl)(5). Additionally, CuCl2·2H2O reacts with the mixture of GeO2, Na2WO4·2H2O, H 2SiW12O40·2H2O 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: [Cu I(2,2′-bpy)(4,4′-bpy)]2[Cu2 I(2,2′-bpy)2(4,4′-bpy)]2[Cu 2ICu6I(2,2′-bpy) 2(4,4′-bpy)2(B-α-GeW9O 34)2)]·2H2O (6). 1, 2, and 3 are discrete dimers constructed from two trivacant Keggin [B-α-XW 9O34]10- (X = GeIV/SiIV) fragments and an octa-Cu cluster whereas 4 displays the 3D (3,6)-connected nets with (4·62)-(42·64·8 7·102) 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 [Cu 2II(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 [Cu2 I-(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.
KW - Copper
KW - Keggin structure
KW - Metal-oxo cluster
KW - Octanuclear copper
KW - Polyoxometaiates
UR - http://www.scopus.com/inward/record.url?scp=55049125239&partnerID=8YFLogxK
U2 - 10.1002/chem.200800856
DO - 10.1002/chem.200800856
M3 - Article
AN - SCOPUS:55049125239
SN - 0947-6539
VL - 14
SP - 9223
EP - 9239
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 30
ER -