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Engineering geometric metamorphosis in {P_(6)M_(2)Mo_(16)O_(73)}-based high-nuclearity metal superclusters: from tetrahedral to square assemblies via topological transformations
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作者 Xiaoyan Zhang Hui Li +2 位作者 Na Xu Xiaodong Liu Xiu-Li Wang 《Inorganic Chemistry Frontiers》 2025年第11期3823-3832,共10页
The synthesis of superclusters is vital for understanding their self-assembly mechanisms,requiring precise control over composition,orientation,and connectivity.The tenets of reticular chemistry afford a systematic ap... The synthesis of superclusters is vital for understanding their self-assembly mechanisms,requiring precise control over composition,orientation,and connectivity.The tenets of reticular chemistry afford a systematic approach to the architectural design and regulation of molecular entities,thereby enabling the fulfillment of preconceived structural objectives.Herein,the strategic introduction of transition metal ions,CoⅡand NiⅡ,has enabled the controlled formation of two novel closely related anionic superclusters based on the{Sr⊂P_(6)M_(2)Mo_(16)O_(73)}clusters:Co_(12)Sr_(4)Mo_(80)P_(36)(1)and Na_(4)Ni_(23)Sr_(4)Mo_(88)P_(52)(2).The former manifests a tetrahedral structure,while the latter,derived from topological transformations of cluster 1,exhibits a unique square geometry.Structural elucidation revealed that the integration of MoV ions in a reduced state,in concert with distinct transition metal ions(CoⅡ and NiⅡ),plays a pivotal role in determining the geometric profiles of these superclusters.Furthermore,clusters 1 and 2 demonstrate efficacy as heterogeneous catalysts,significantly promoting the transformation of methyl phenyl sulfide(MPS)to methyl phenyl sulfoxide(MPSO). 展开更多
关键词 architectural design regulation molecular entitiesthereby reticular chemistry anionic superclust high nuclearity metal superclusters transition metal ionsco fulfillment preconceived structural objectiveshereinthe geometric metamorphosis synthesis superclusters
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