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+). Issue 11 (26th February 2021)

• Record Type: Journal Article
• Authors: Haider, Ali; Bassil, Bassem S.; Lin, Zhengguo; Ma, Xiang; Haferl, Peter J.; Bindra, Jasleen K.; Kinyon, Jared; Zhang, Guangjin; Keita, Bineta; Dalal, Naresh S.; Kortz, Ulrich
• Is Part Of: Dalton transactions. Volume 50:Issue 11(2021)
• Page Start: 3923
• Page End: 3930
• Publication Date: 2021-02-26
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d0dt03392h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Three novel heteropolytungstates, [M II 4 (OH)3 (H2 O)2 (α-SiW10 O36.5 )2 ] 13− (M = Co, Ni, and Zn), were synthesized and structurally characterized, and magnetic and electrochemical studies are presented. Abstract : Interaction of the trilacunary 9-tungstosilicate [ A -α-SiW9 O34 ] 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 (H2 O)2 (α-SiW10 O36.5 )2 ] 13− (M = Co 2+ (1 ), Ni 2+ (2 ), and Zn 2+ (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 Co 2+ ions in 1 can be oxidized to Co 3+ 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.