| Cluster-based metal chalocigenides are a new type of functional materials and have attracted extensive attention in the field of gas adsorption,ion exchange,photoelectrocatalysis and photoluminescence due to the integration of semiconducting with porosity.Such cluster-based materials are not only ideal models for studying the bottom-up assembly of clusters,but also can facilitate the exploration of the precise structure-activity relationship due to the characteristics of the accurate structure and the adjustable multi-components in clusters.Therefore,it is of great significance to construct new cluster-based metal chalcogenide materials.Metal component plays a key role in controlling the size of cluster and type of framework.Previous studies on metal composition of clusters focused on the mixed metal systems,such as M+/2+/M3+or M3+/M4+.Among them,Sn4+ ion usually occupies the corner site of the cluster,which not only plays a good regulatory role in controlling the local charge of terminal S2-,but also helps to reduce the overall negative charge of the cluster.However,the cases with high-valence Sn4+ ions locating in large-sized clusters were reported.To explore the influence of the introduction of high-valent Sn4+on the structure and performance of the frameworks related to the large-sizes clusters,the mixed metal strategy was developed to realize the framework materials with large-sized clusters as the building block and the electrochemical and photoluminescent properties were also explored.The main contents are discribled as follow:1.Chalcogenide frameworks constructed from P2-CuInSnS cluster and their photo-/electrical propertiesBy virtue of the mixed-metal(M+/M3+/M4+)synthetic strategy,we successfully obtained two three-dimensional frameworks,i.e.MCOF-1[Cu6.2In10.6Sn9.2S42.5]and MCOF-2[Cu6In12.5Sn7.5S42],which are assembled by large-sized P2-CuInSnS clusters in different packing modes.Due to the difference in the atomic number of high-valent Sn4+ions in two compounds,the coordination ability of S2-at the corner of cluster is different.MCOF-1 constructed from ?3-P2 clusters has a srs topology,while MCOF-2 constructed from ?4-P2 clusters has a diamond topology.By comparing the photoelectric response and oxygen reduction performance,MCOF-2 exhibited a relatively faster photocurrent response,better reproducibility and higher electrocatalytic oxygen reduction activity than MCOF-1.This work basically shows that cluster-based chalcogenide frameworks with high connectivity of clusters have faster electron transport efficiencies between adjacent clusters than that with low-connectivity of the same clusters.2.Chalcogenide frameworks built with single Cu ion as a linker and their non-enzymatic glucose detectionTwo cluster-based crystalline chalcogenides(MCOF-3 and MCOF-4)were synthesized through the mixed metal strategy.The triple interpenetrated dia topology of MCOF-3 and MCOF-4 are constructed from P2([Cu8.5Ga11Sn8.5S44])and T4([Cu5Ga12Sn5S35])clusters as secondary building units and single copper ion as connecting units,respectively.The two cluster-based chalcogenides also showed high activity for non-enzymic glucose sensing.3.Chalcogenide frameworks constructed from T3-SnOS clusters and their photoluminescence performanceThree metal chalcogenides based on T3-SnOS cluster were constructed with the structural formulae of[Sn]2[Sn40O16S74](1),[Sn40O16S73](2),and[Sn][Sn40O16S74](3).It should be noted that Sn element not only participates in the construction of clusters,but also acts as a connecting units for framework extension in compounds 1 and 3.In compounds 2 and 3,the interrupted T3,2 clusters was for the first time observed.In addition,compound 2 is the first case that displays photoluminescence emission among T3-SnOS-based chalcogenides.Current results enrich the structure system of cluster-based chalcogenide frameworks,and provide theoretical guidance for the construction and performance research of subsequent chalcogenide-based crystalline materials. |
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