A nanoscale ferromagnetic nickel-supercluster functionalized giant heterometallic arsenototungstate with ability in catalyzing reactive oxygen species generation

• Published in: Journal of molecular structure 2023-11, Vol.1291, p.136010, Article 136010
• Main Authors: Ma, Xiang, Sun, Yusheng, Lu, Qinli, Bai, Xinqi, Zang, Qijiao, Yan, Xiuwen, Wang, Feng, Hua, Jiai
• Format: Article
• Language: English
• Subjects: Artificial oxidase; Giant heterometallic arsenototungstate; High-nuclear TM cluster; Nanoenzyme; Reactive oxygen species
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2023.136010

•[Na(H2O)5]2[Ni(H2O)(en)2]2[Ni(H2O)3(en)][H4Ni6(OH)2(en)2.5(B-α-AsVW9O34)]2[W4O16][Ni4(H2O)2(en)2]2[Ni(H2O)(en)][(α-AsVW6O26)]2·3H2O (abbreviated as NiAW, en = ethylenediamine). represents a novel high nuclear nickel cluster functionalized giant heterometallic arsenototungstate.•The synthetic method of NiAW will serve as a good example for subsequent synthesis and formation of such high nuclear cluster containing POMs.•NiAW can catalyze the production of reactive oxygen species (ROS) in water phase efficiently. In this work, a high-nuclear functionalized giant heterometallic arsenototungstate with artificial oxidase property, [Na(H2O)5]2[Ni(H2O)(en)2]2[Ni(H2O)3(en)][H4Ni6 (OH)2(en)2.5(B-α-AsVW9O34)]2[W4O16][Ni4(H2O)2(en)2]2[Ni(H2O)(en)][(α-AsVW6O26)]2·3H2O (abbreviated as NiAW, en = ethylenediamine) has been designed and synthesized successfully. NiAW was structurally characterized by X-ray photoelectron spectrum (XPS), infrared (IR) spectrum, ultraviolet-visible (UV-vis) spectrum, single-crystal X-ray diffraction (SXRD) and bond valence sums (Σs) calculation. The SXRD results indicated that the skeleton of NiAW is constructed by two sandwich-type [(B-α-AsVW9O34)H4Ni6(OH)2(en)2.5(α-AsVW6O26)]4– sub-unit linking by a [W4O16]8– building block, in which a novel tetra-Ni cluster [Ni4(H2O)2(en)2O10]12– graft to the hexa-vacant Keggin [α-AsW6O26]11– fragment. Finally, with the embellishment of several [Ni(en)2(H2O)]2+, [Ni(en)(H2O)]2+, and [Na(H2O)5]+ cations, NiAW forms its complete structure. Notably, the Ni-cluster in NiAW exhibited the ferromagnetic coupling interactions. Furthermore, it is also demonstrated that NiAW is capable of catalyzing the generation of ROS efficiently by the synergistic effects of POM fragments and nickel complexes.