Two Series of CuII-Substituted Sandwich-Type Polyoxotungstates Constructed from Trivacant Germanotungstate Fragments

Zhong Zhang; Ke Ning Sun; Guo Yu Yang

doi:10.1002/slct.201901273

Two Series of Cu^II-Substituted Sandwich-Type Polyoxotungstates Constructed from Trivacant Germanotungstate Fragments

Zhong Zhang, Ke Ning Sun, Guo Yu Yang^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

Under hydrothermal conditions, two families of new Cu^II-substituted sandwich-type germanotungstates (GTs): Cu₆-GTs (enH₂)₂[Cu(en)₂]₂[Cu₆(en)₂(H₂O)₂(B-α-GeW₉O₃₄)₂]⋅4H₂O (1), H₄[Cu(deta)(H₂O)]₂[Cu₆(en)₂(H₂O)₂(B-GeW₉O₃₄)₂]⋅8H₂O (2), [Cu(en)(H₂O)₂]₂[Cu(en)₂]₂[Cu₆(en)₂(H₂O)₂(B-α-GeW₉O₃₄)₂]⋅8H₂O (3) (en=ethylenediamine, deta=diethylenetriamine) and Cu₄-GTs H₄[Cu(H₂O)₄]₂[Cu(H₂O)₅]₂[Cu₄(H₂O)₂(B-α-GeW₉O₃₄)₂]⋅8H₂O (4), H₁₀[Cu(H₂O)₃(Cl)]₂[Cu₄(B-α-GeW₉O₃₄)₂]⋅8H₂O (5), H₈[Na(H₂O)₄]₂[Cu(H₂O)₃(Cl)]₂[Cu₄(B-α-GeW₉O₃₄)₂]⋅8H₂O (6) have been made and characterized. Single-crystal structural analyses indicate that 1–3 contain a belt-like hexa-Cu^II substituted sandwich-type [Cu₆(en)₂(H₂O)₂(B-α-GeW₉O₃₄)₂]⁸⁺ unit. Notably, 1–3 are rare organic-inorganic hybrid polyoxometalates with [Cu₆(en)₂(H₂O)₂(B-α-GeW₉O₃₄)₂]⁸⁻ subunits, displaying the assembly from 1-D chain to 3-D framework by the [Cu(en)₂]²⁺ or [Cu(deta)₂(H₂O)]²⁺ linkers. 4–6 contain rhomb-like tetra-Cu^II substituted sandwich-type [Cu₄(H₂O)_n(B-α-GeW₉O₃₄)₂]¹²⁻ (n=2, 0) units linked by [Cu(H₂O)₄]²⁺ or [Cu₂(H₂O)₆Cl₂]⁺ clusters to from 1-D chain. Magnetic measurements performed on 3 indicate the occurrence of ferromagnetic interactions within the copper ions. Furthermore, the electrochemical and electro-catalysis properties of 3 have been studied in 0.02 M H₂SO₄ + 0.5 M Na₂SO₄ solution, and show good electro-catalytic activity to the reduction of nitrite.

Original language	English
Pages (from-to)	7559-7565
Number of pages	7
Journal	ChemistrySelect
Volume	4
Issue number	25
DOIs	https://doi.org/10.1002/slct.201901273
Publication status	Published - 5 Jul 2019

Keywords

Cu-substituted
germanotungstate
polyoxometalates
sandwich-type

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10.1002/slct.201901273

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@article{6522ea685faa4820a54936056885fbb4,

title = "Two Series of CuII-Substituted Sandwich-Type Polyoxotungstates Constructed from Trivacant Germanotungstate Fragments",

abstract = "Under hydrothermal conditions, two families of new CuII-substituted sandwich-type germanotungstates (GTs): Cu6-GTs (enH2)2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅4H2O (1), H4[Cu(deta)(H2O)]2[Cu6(en)2(H2O)2(B-GeW9O34)2]⋅8H2O (2), [Cu(en)(H2O)2]2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅8H2O (3) (en=ethylenediamine, deta=diethylenetriamine) and Cu4-GTs H4[Cu(H2O)4]2[Cu(H2O)5]2[Cu4(H2O)2(B-α-GeW9O34)2]⋅8H2O (4), H10[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (5), H8[Na(H2O)4]2[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (6) have been made and characterized. Single-crystal structural analyses indicate that 1–3 contain a belt-like hexa-CuII substituted sandwich-type [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8+ unit. Notably, 1–3 are rare organic-inorganic hybrid polyoxometalates with [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8− subunits, displaying the assembly from 1-D chain to 3-D framework by the [Cu(en)2]2+ or [Cu(deta)2(H2O)]2+ linkers. 4–6 contain rhomb-like tetra-CuII substituted sandwich-type [Cu4(H2O)n(B-α-GeW9O34)2]12− (n=2, 0) units linked by [Cu(H2O)4]2+ or [Cu2(H2O)6Cl2]+ clusters to from 1-D chain. Magnetic measurements performed on 3 indicate the occurrence of ferromagnetic interactions within the copper ions. Furthermore, the electrochemical and electro-catalysis properties of 3 have been studied in 0.02 M H2SO4 + 0.5 M Na2SO4 solution, and show good electro-catalytic activity to the reduction of nitrite.",

keywords = "Cu-substituted, germanotungstate, polyoxometalates, sandwich-type",

author = "Zhong Zhang and Sun, {Ke Ning} and Yang, {Guo Yu}",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = jul,

day = "5",

doi = "10.1002/slct.201901273",

language = "English",

volume = "4",

pages = "7559--7565",

journal = "ChemistrySelect",

issn = "2365-6549",

publisher = "Wiley-Blackwell Publishing Ltd",

number = "25",

}

TY - JOUR

T1 - Two Series of CuII-Substituted Sandwich-Type Polyoxotungstates Constructed from Trivacant Germanotungstate Fragments

AU - Zhang, Zhong

AU - Sun, Ke Ning

AU - Yang, Guo Yu

PY - 2019/7/5

Y1 - 2019/7/5

N2 - Under hydrothermal conditions, two families of new CuII-substituted sandwich-type germanotungstates (GTs): Cu6-GTs (enH2)2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅4H2O (1), H4[Cu(deta)(H2O)]2[Cu6(en)2(H2O)2(B-GeW9O34)2]⋅8H2O (2), [Cu(en)(H2O)2]2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅8H2O (3) (en=ethylenediamine, deta=diethylenetriamine) and Cu4-GTs H4[Cu(H2O)4]2[Cu(H2O)5]2[Cu4(H2O)2(B-α-GeW9O34)2]⋅8H2O (4), H10[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (5), H8[Na(H2O)4]2[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (6) have been made and characterized. Single-crystal structural analyses indicate that 1–3 contain a belt-like hexa-CuII substituted sandwich-type [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8+ unit. Notably, 1–3 are rare organic-inorganic hybrid polyoxometalates with [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8− subunits, displaying the assembly from 1-D chain to 3-D framework by the [Cu(en)2]2+ or [Cu(deta)2(H2O)]2+ linkers. 4–6 contain rhomb-like tetra-CuII substituted sandwich-type [Cu4(H2O)n(B-α-GeW9O34)2]12− (n=2, 0) units linked by [Cu(H2O)4]2+ or [Cu2(H2O)6Cl2]+ clusters to from 1-D chain. Magnetic measurements performed on 3 indicate the occurrence of ferromagnetic interactions within the copper ions. Furthermore, the electrochemical and electro-catalysis properties of 3 have been studied in 0.02 M H2SO4 + 0.5 M Na2SO4 solution, and show good electro-catalytic activity to the reduction of nitrite.

AB - Under hydrothermal conditions, two families of new CuII-substituted sandwich-type germanotungstates (GTs): Cu6-GTs (enH2)2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅4H2O (1), H4[Cu(deta)(H2O)]2[Cu6(en)2(H2O)2(B-GeW9O34)2]⋅8H2O (2), [Cu(en)(H2O)2]2[Cu(en)2]2[Cu6(en)2(H2O)2(B-α-GeW9O34)2]⋅8H2O (3) (en=ethylenediamine, deta=diethylenetriamine) and Cu4-GTs H4[Cu(H2O)4]2[Cu(H2O)5]2[Cu4(H2O)2(B-α-GeW9O34)2]⋅8H2O (4), H10[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (5), H8[Na(H2O)4]2[Cu(H2O)3(Cl)]2[Cu4(B-α-GeW9O34)2]⋅8H2O (6) have been made and characterized. Single-crystal structural analyses indicate that 1–3 contain a belt-like hexa-CuII substituted sandwich-type [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8+ unit. Notably, 1–3 are rare organic-inorganic hybrid polyoxometalates with [Cu6(en)2(H2O)2(B-α-GeW9O34)2]8− subunits, displaying the assembly from 1-D chain to 3-D framework by the [Cu(en)2]2+ or [Cu(deta)2(H2O)]2+ linkers. 4–6 contain rhomb-like tetra-CuII substituted sandwich-type [Cu4(H2O)n(B-α-GeW9O34)2]12− (n=2, 0) units linked by [Cu(H2O)4]2+ or [Cu2(H2O)6Cl2]+ clusters to from 1-D chain. Magnetic measurements performed on 3 indicate the occurrence of ferromagnetic interactions within the copper ions. Furthermore, the electrochemical and electro-catalysis properties of 3 have been studied in 0.02 M H2SO4 + 0.5 M Na2SO4 solution, and show good electro-catalytic activity to the reduction of nitrite.

KW - Cu-substituted

KW - germanotungstate

KW - polyoxometalates

KW - sandwich-type

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DO - 10.1002/slct.201901273

M3 - Article

AN - SCOPUS:85068434157

SN - 2365-6549

VL - 4

SP - 7559

EP - 7565

JO - ChemistrySelect

JF - ChemistrySelect

IS - 25

ER -

Two Series of Cu^II-Substituted Sandwich-Type Polyoxotungstates Constructed from Trivacant Germanotungstate Fragments

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