Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters

Jun Wei Zhao; Chun Mei Wang; Jie Zhang; Shou Tian Zheng; Guo Yu Yang

doi:10.1002/chem.200800856

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters

Jun Wei Zhao
, Chun Mei Wang
, Jie Zhang
, Shou Tian Zheng
, Guo Yu Yang^*

^*此作品的通讯作者

CAS - Fujian Institute of Research on the Structure of Matter
Harbin Normal University

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203 引用（Scopus）

摘要

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[Cu₈^II(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[Cu₈^II(en)₄(H ₂O)₂(B-α-SiW₉-O₃₄) ₂]·8H₂O (3), [Cu^II(H₂O) ₂]H₂:[Cu₈^II-(en)₄(H ₂O)₂(B-α-SiW₉O₃₄) ₂] (4), and [Cu₂^II(H₂O) ₂(2,2′-bpy)₂]{[Cu^II(bdyl)] ₂-[Cu₈^II(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 ₂^ICu₆^I(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 = Ge^IV/Si^IV) 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 ₂^II(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 Cu^I-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.

源语言	英语
页（从-至）	9223-9239
页数	17
期刊	Chemistry - A European Journal
卷	14
期	30
DOI	https://doi.org/10.1002/chem.200800856
出版状态	已出版 - 20 10月 2008
已对外发布	是

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@article{ad44d5ba573345baa499083c88e0efcd,

title = "Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters",

abstract = "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.",

keywords = "Copper, Keggin structure, Metal-oxo cluster, Octanuclear copper, Polyoxometaiates",

author = "Zhao, \{Jun Wei\} and Wang, \{Chun Mei\} and Jie Zhang and Zheng, \{Shou Tian\} and Yang, \{Guo Yu\}",

year = "2008",

month = oct,

day = "20",

doi = "10.1002/chem.200800856",

language = "English",

volume = "14",

pages = "9223--9239",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

number = "30",

}

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters. / Zhao, Jun Wei; Wang, Chun Mei; Zhang, Jie 等.
在: Chemistry - A European Journal, 卷 14, 号码 30, 20.10.2008, 页码 9223-9239.

科研成果: 期刊稿件 › 文章 › 同行评审

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 - https://www.scopus.com/pages/publications/55049125239

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 -

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions: IX. A series of novel polyoxotungstates sandwiched by octa-copper clusters

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