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
基金financially supported by the National Natural Science Foundation of China(No.22271021,21971024,22201021,22101030).
文摘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).