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Title: Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

Abstract

Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen){sub 2}]{sub 2}{l_brace}[Cu(phen)]{sub 2} [SiMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace} (1), {l_brace}[Zn(phen){sub 2}]{sub 2}[GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Zn(phen){sub 2}(H{sub 2}O)]{sub 2} [GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.3H{sub 2}O (2) and {l_brace}[Co(phen){sub 2}]{sub 2}[PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Co(phen){sub 2}(OH)]{sub 2} [PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.2.5H{sub 2}O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo{sub 12}O{sub 4}(VO){sub 2}]{sup 2-} linked to two [Cu(phen)]{sup +} complexes with two [Cu(phen){sub 2}]{sup +} countercations. Compound 2 contains two bicapped Keggin anions [GeMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-}, one linked to two [Zn(phen){sub 2}(H{sub 2}O)]{sup 2+} cations and the other one linked to two [Zn(phen){sub 2}]{sup 2+} cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution frommore » the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions. -- Graphical abstract: Three new Keggin polyoxometalate-based compounds have been synthesized under hydrothermal condition. These three compounds present the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P) as building blocks. Among the three compounds, compound 3 is a two-dimensional polyoxometalate-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers.« less

Authors:
 [1];  [2];  [3];  [3];  [1]
  1. Institute of Polyoxometalate Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China)
  2. Institute of Polyoxometalate Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China). E-mail: jpeng@nenu.edu.cn
  3. Instituto de Ciencia Molecular, Universidad de Valencia. Pol. La Coma s/n 46980 Paterna, Valencia (Spain)
Publication Date:
OSTI Identifier:
20784856
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2005.09.051; PII: S0022-4596(05)00438-X; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COBALT COMPLEXES; COPPER COMPLEXES; CRYSTAL STRUCTURE; HYDROTHERMAL SYNTHESIS; PARAMAGNETISM; ZINC COMPLEXES

Citation Formats

Shi Zhenyu, Peng Jun, Gomez-Garcia, Carlos J., Benmansour, Samia, and Gu Xiaojun. Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties. United States: N. p., 2006. Web.
Shi Zhenyu, Peng Jun, Gomez-Garcia, Carlos J., Benmansour, Samia, & Gu Xiaojun. Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties. United States.
Shi Zhenyu, Peng Jun, Gomez-Garcia, Carlos J., Benmansour, Samia, and Gu Xiaojun. Sun . "Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties". United States. doi:.
@article{osti_20784856,
title = {Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties},
author = {Shi Zhenyu and Peng Jun and Gomez-Garcia, Carlos J. and Benmansour, Samia and Gu Xiaojun},
abstractNote = {Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen){sub 2}]{sub 2}{l_brace}[Cu(phen)]{sub 2} [SiMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace} (1), {l_brace}[Zn(phen){sub 2}]{sub 2}[GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Zn(phen){sub 2}(H{sub 2}O)]{sub 2} [GeMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.3H{sub 2}O (2) and {l_brace}[Co(phen){sub 2}]{sub 2}[PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}{l_brace}[Co(phen){sub 2}(OH)]{sub 2} [PMo{sub 12}O{sub 4}(VO){sub 2}]{r_brace}.2.5H{sub 2}O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo{sub 12}O{sub 4}(VO){sub 2}]{sup 2-} linked to two [Cu(phen)]{sup +} complexes with two [Cu(phen){sub 2}]{sup +} countercations. Compound 2 contains two bicapped Keggin anions [GeMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-}, one linked to two [Zn(phen){sub 2}(H{sub 2}O)]{sup 2+} cations and the other one linked to two [Zn(phen){sub 2}]{sup 2+} cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions. -- Graphical abstract: Three new Keggin polyoxometalate-based compounds have been synthesized under hydrothermal condition. These three compounds present the bicapped Keggin anions [XMo{sub 12}O{sub 4}(VO){sub 2}] (X=Si, Ge and P) as building blocks. Among the three compounds, compound 3 is a two-dimensional polyoxometalate-based square network formed by bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}]{sup 4-} connected by [Co(phen){sub 2}]{sup 2+} cations. Discrete bicapped Keggin anions [PMo{sub 12}O{sub 4}(VO){sub 2}] linked to two [Co(phen){sub 2}(OH)]{sup +} cations are located between the layers.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 179,
place = {United States},
year = {Sun Jan 15 00:00:00 EST 2006},
month = {Sun Jan 15 00:00:00 EST 2006}
}
  • Three novel organic-inorganic hybrid borotungstates {l_brace}[Ni(phen){sub 2}(H{sub 2}O)]{sub 2}H(alpha-BW{sub 12}O{sub 40}){r_brace}.4H{sub 2}O (1), [Cu{sup I}(2,2'-bipy)(4,4'-bipy){sub 0.5}]{sub 2}{l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2} (alpha-BW{sub 12}O{sub 40}){r_brace} (2) and {l_brace}[Cu{sup I}(4,4'-bipy)]{sub 3}H{sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace}.3.5H{sub 2}O (3) (phen=1,10-phenanthroline, 2,2'-bipy=2,2'-bipyridine, 4,4'-bipy=4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and photoluminescence. The structural analysis reveals that 1 consists of a 0-D bisupporting polyoxometalate cluster where two [Ni(phen){sub 2}(H{sub 2}O)]{sup 2+} cations are grafted on the polyoxoanion [alpha-BW{sub 12}O{sub 40}]{sup 5-} through two terminal oxygen atoms,more » 2 shows a 1-D infinite chain constructed from [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanions and {l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2}{r_brace}{sup 3+} cations by means of alternating fashion, and 3 displays an unprecedented 2D extended structure built by [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanions and -Cu{sup I}-4,4'-bipy- linear chains, in which each [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanion acts as a tetradentate inorganic ligand and provides three terminal oxygen atom and one two-bridging oxygen atom. The presence of Ni{sup II} and W{sup VI} in 1, Cu{sup I} ions and W{sup VI} in 2 and 3 are identified by XPS spectra. The photoluminescence of 2 and 3 are also investigated. - Graphical abstract: Three novel organic-inorganic hybrid borotungstates {l_brace}[Ni(phen){sub 2}(H{sub 2}O)]{sub 2}H(alpha-BW{sub 12}O{sub 40}){r_brace}.4H{sub 2}O (1), [Cu{sup I}(2,2'-bipy) (4,4'-bipy){sub 0.5}]{sub 2}{l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace} (2) and {l_brace}[Cu{sup I}(4,4'-bipy)]{sub 3}H{sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace}.3.5H{sub 2}O (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analyses, X-ray photoelectron spectroscopy and photoluminescence.« less
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