Ni II 36 ‐Containing 54‐Tungsto‐6‐Silicate: Synthesis, Structure, Magnetic and Electrochemical Studies

• Published in: Chemistry : a European journal Vol. 27; no. 61; pp. 15081 - 15085
• Main Authors: Goura, Joydeb, Bassil, Bassem S., Ma, Xiang, Rajan, Ananthu, Moreno‐Pineda, Eufemio, Schnack, Jürgen, Ibrahim, Masooma, Powell, Annie K., Ruben, Mario, Wang, Jingjing, Ruhlmann, Laurent, Kortz, Ulrich
• Format: Journal Article
• Language: English
• Published: Wiley-VCH Verlag 02.11.2021
• Subjects: Chemical Sciences; Inorganic chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202102973

Abstract The 36‐Ni II ‐containing 54‐tungsto‐6‐silicate, [Ni 36 (OH) 18 (H 2 O) 36 (SiW 9 O 34 ) 6 ] 6− ( Ni 36 ) was synthesized by a simple one‐pot reaction of the Ni 2 ‐pivalate complex [Ni 2 ( μ ‐OH 2 )(O 2 CCMe 3 ) 4 (HO 2 CCMe 3 ) 4 ] with the trilacunary [SiW 9 O 34 ] 10− polyanion precursor in water and structurally characterized by a multitude of physicochemical techniques including single‐crystal XRD, FTIR, TGA, elemental analysis, magnetic and electrochemical studies. Polyanion Ni 36 comprises six equivalent {Ni II 6 SiW 9 } units which are linked by Ni−O−W bridges forming a macrocyclic assembly. Magnetic studies demonstrate that the {Ni 6 } building blocks in Ni 36 remain magnetically intact while forming a hexagonal ring with antiferromagnetic exchange interactions between adjacent {Ni 6 } units. Electrochemical studies indicate that the first reduction is reversible and associated with the W VI/V couple, whereas the second reduction is irreversible attributed to the Ni II/0 couple.