Cupric siliconiobate. Synthesis and solid-state studies of a pseudosandwich-type heteropolyanion

Travis M. Anderson; Todd M. Alam; Mark A. Rodriguez; Joel N. Bixler; Wenqian Xu; John B. Parise; May Nyman

doi:10.1021/ic800860q

Cupric siliconiobate. Synthesis and solid-state studies of a pseudosandwich-type heteropolyanion

Travis M. Anderson
, Todd M. Alam
, Mark A. Rodriguez
, Joel N. Bixler
, Wenqian Xu
, John B. Parise
, May Nyman

Geosciences

Sandia National Laboratories, New Mexico
Stony Brook University

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

25 Scopus citations

Abstract

The Na⁺ and [Cu(en)₂(H₂O) ₂]²⁺ (en = ethylenediamine) salt of a pseudosandwich-type heteropolyniobate forms upon prolonged heating of Cu(NO₃)₂ and hydrated Na₁₄[(SiOH)₂Si₂Nb ₁₆O₅₄] in a mixed water-en solution. The structure [a = 14.992(2) Å, b = 25.426(4) Å, c = 30.046(4) Å, orthorhombic, Pnn2, R1 = 6.04%, based on 25869 unique reflections] consists of two [Na(SiOH)₂Si₂Nb₁₆O₅₄]^13- units linked by six sodium cations, and this sandwich is charge-balanced by five [Cu(en)₂(H₂O)₂]²⁺ complexes, seven protons, and three additional sodium atoms (all per a sandwich-type cluster). Diffuse-reflectance UV-vis indicates that there is a λ_max at 383 nm for the Cu^II d-d transition and the ²⁹Si MAS NMR spectrum has two peaks at -78.2 ppm (151 Hz) and -75.5 ppm (257 Hz) for the two pairs of symmetry-equivalent internal [SiO₄]^4- and external [SiO₃(OH)]^3- tetrahedra, respectively. Unlike tungsten-based sandwich-type complexes, the [Na(SiOH)₂Si ₂Nb₁₆O₅₄]^13- units are linked exclusively by Na⁺ instead of one or more d-electron metals.

Original language	English
Pages (from-to)	7834-7839
Number of pages	6
Journal	Inorganic Chemistry
Volume	47
Issue number	17
DOIs	https://doi.org/10.1021/ic800860q
State	Published - Sep 1 2008

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@article{ff0e67eb86ae438e9512d5fefc5140c5,

title = "Cupric siliconiobate. Synthesis and solid-state studies of a pseudosandwich-type heteropolyanion",

abstract = "The Na+ and [Cu(en)2(H2O) 2]2+ (en = ethylenediamine) salt of a pseudosandwich-type heteropolyniobate forms upon prolonged heating of Cu(NO3)2 and hydrated Na14[(SiOH)2Si2Nb 16O54] in a mixed water-en solution. The structure [a = 14.992(2) {\AA}, b = 25.426(4) {\AA}, c = 30.046(4) {\AA}, orthorhombic, Pnn2, R1 = 6.04\%, based on 25869 unique reflections] consists of two [Na(SiOH)2Si2Nb16O54]13- units linked by six sodium cations, and this sandwich is charge-balanced by five [Cu(en)2(H2O)2]2+ complexes, seven protons, and three additional sodium atoms (all per a sandwich-type cluster). Diffuse-reflectance UV-vis indicates that there is a λmax at 383 nm for the CuII d-d transition and the 29Si MAS NMR spectrum has two peaks at -78.2 ppm (151 Hz) and -75.5 ppm (257 Hz) for the two pairs of symmetry-equivalent internal [SiO4]4- and external [SiO3(OH)]3- tetrahedra, respectively. Unlike tungsten-based sandwich-type complexes, the [Na(SiOH)2Si 2Nb16O54]13- units are linked exclusively by Na+ instead of one or more d-electron metals.",

author = "Anderson, \{Travis M.\} and Alam, \{Todd M.\} and Rodriguez, \{Mark A.\} and Bixler, \{Joel N.\} and Wenqian Xu and Parise, \{John B.\} and May Nyman",

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T1 - Cupric siliconiobate. Synthesis and solid-state studies of a pseudosandwich-type heteropolyanion

AU - Anderson, Travis M.

AU - Alam, Todd M.

AU - Rodriguez, Mark A.

AU - Bixler, Joel N.

AU - Xu, Wenqian

AU - Parise, John B.

AU - Nyman, May

PY - 2008/9/1

Y1 - 2008/9/1

N2 - The Na+ and [Cu(en)2(H2O) 2]2+ (en = ethylenediamine) salt of a pseudosandwich-type heteropolyniobate forms upon prolonged heating of Cu(NO3)2 and hydrated Na14[(SiOH)2Si2Nb 16O54] in a mixed water-en solution. The structure [a = 14.992(2) Å, b = 25.426(4) Å, c = 30.046(4) Å, orthorhombic, Pnn2, R1 = 6.04%, based on 25869 unique reflections] consists of two [Na(SiOH)2Si2Nb16O54]13- units linked by six sodium cations, and this sandwich is charge-balanced by five [Cu(en)2(H2O)2]2+ complexes, seven protons, and three additional sodium atoms (all per a sandwich-type cluster). Diffuse-reflectance UV-vis indicates that there is a λmax at 383 nm for the CuII d-d transition and the 29Si MAS NMR spectrum has two peaks at -78.2 ppm (151 Hz) and -75.5 ppm (257 Hz) for the two pairs of symmetry-equivalent internal [SiO4]4- and external [SiO3(OH)]3- tetrahedra, respectively. Unlike tungsten-based sandwich-type complexes, the [Na(SiOH)2Si 2Nb16O54]13- units are linked exclusively by Na+ instead of one or more d-electron metals.

AB - The Na+ and [Cu(en)2(H2O) 2]2+ (en = ethylenediamine) salt of a pseudosandwich-type heteropolyniobate forms upon prolonged heating of Cu(NO3)2 and hydrated Na14[(SiOH)2Si2Nb 16O54] in a mixed water-en solution. The structure [a = 14.992(2) Å, b = 25.426(4) Å, c = 30.046(4) Å, orthorhombic, Pnn2, R1 = 6.04%, based on 25869 unique reflections] consists of two [Na(SiOH)2Si2Nb16O54]13- units linked by six sodium cations, and this sandwich is charge-balanced by five [Cu(en)2(H2O)2]2+ complexes, seven protons, and three additional sodium atoms (all per a sandwich-type cluster). Diffuse-reflectance UV-vis indicates that there is a λmax at 383 nm for the CuII d-d transition and the 29Si MAS NMR spectrum has two peaks at -78.2 ppm (151 Hz) and -75.5 ppm (257 Hz) for the two pairs of symmetry-equivalent internal [SiO4]4- and external [SiO3(OH)]3- tetrahedra, respectively. Unlike tungsten-based sandwich-type complexes, the [Na(SiOH)2Si 2Nb16O54]13- units are linked exclusively by Na+ instead of one or more d-electron metals.

UR - https://www.scopus.com/pages/publications/51849115893

U2 - 10.1021/ic800860q

DO - 10.1021/ic800860q

M3 - Article

AN - SCOPUS:51849115893

SN - 0020-1669

VL - 47

SP - 7834

EP - 7839

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -

Cupric siliconiobate. Synthesis and solid-state studies of a pseudosandwich-type heteropolyanion

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