Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M4(OH)3(H2O)2(α-SiW10O36.5)2]13− (M = Co2+, Ni2+, and Zn2+)

Ali Haider; Bassem S. Bassil; Zhengguo Lin; Xiang Ma; Peter J. Haferl; Jasleen K. Bindra; Jared Kinyon; Guangjin Zhang; Bineta Keita; Naresh S. Dalal; Ulrich Kortz

doi:10.1039/D0DT03392H

Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M₄(OH)₃(H₂O)₂(α-SiW₁₀O_36.5)₂]¹³⁻ (M = Co²⁺, Ni²⁺, and Zn²⁺)†

Ali Haider,

^ab Bassem S. Bassil,

^ac Zhengguo Lin,

^ad Xiang Ma,

^a Peter J. Haferl,^a Jasleen K. Bindra,

^e Jared Kinyon,

^e Guangjin Zhang,

^f Bineta Keita,^g Naresh S. Dalal

^e and Ulrich Kortz

*^a

Author affiliations

* Corresponding authors

^a Jacobs University, Department of Life Sciences and Chemistry, Campus Ring 1, 28759 Bremen, Germany
E-mail: u.kortz@jacobs-university.de
Web: http://ukortz.user.jacobs-university.de

^b Department of Chemistry, Quaid-e-Azam University, Islamabad, Pakistan

^c Department of Chemistry, Faculty of Arts and Sciences, University of Balamand, P.O. Box 100, Tripoli, Lebanon

^d Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China

^e Department of Chemistry and Biochemistry, National High Magnetic Field Laboratory, Florida State University, 1800 E Paul Dirac Drive, Tallahassee, Florida 32306, USA

^f Key Laboratory of Green Process and Engineering, Chinese Academy of Science, Beijing, China

^g Retired from Laboratoire de Chimie-Physique, UMR 8000 CNRS, Université Paris-Sud Orsay, France

Abstract

Interaction of the trilacunary 9-tungstosilicate [A-α-SiW₉O₃₄]¹⁰⁻ with cobalt(II), nickel(II) and zinc(II) ions in pH 9 aqueous medium at room temperature led to the formation of the respective M₄-containing heteropolytungstates [M₄(OH)₃(H₂O)₂(α-SiW₁₀O_36.5)₂]¹³⁻ (M = Co²⁺ (1), Ni²⁺ (2), and Zn²⁺ (3)). Polyanions 1–3 were characterized in the solid state by single-crystal XRD, FT-IR spectroscopy, and thermogravimetric and elemental analyses. Electrochemical studies showed that the Co²⁺ ions in 1 can be oxidized to Co³⁺ and the CVs of the W^VI centers of the polyanions feature well-defined and chemically reversible reduction waves. Magnetic measurements on 1 and 2 showed paramagnetism with complex ferromagnetic and antiferromagnetic interactions. A model was presented for extracting the exchange constants for the magnetic exchange interaction.

Dalton Transactions

Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M₄(OH)₃(H₂O)₂(α-SiW₁₀O_36.5)₂]¹³⁻ (M = Co²⁺, Ni²⁺, and Zn²⁺)†

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Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M₄(OH)₃(H₂O)₂(α-SiW₁₀O_36.5)₂]¹³⁻ (M = Co²⁺, Ni²⁺, and Zn²⁺)

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