Consolidation of 2D Frameworks Based on Corner-Shared Supertetrahedral T5 Clusters via M₂OS₂ Units for Tunable...

Introducing transition metals into the intercluster linkers has been considered an important strategy for the rapid development of metal chalcogenide supertetrahedral (Tn) cluster-based open frameworks with excellent properties. However, using this strategy for achieving the structure and property tunability in the cluster-based framework of Tn (n ≥ 5) is still a great challenge. Herein, we report on three new sulfide and oxosulfide open frameworks of T5 clusters, i.e., T5-ZnMnInOS ([In₃₀Zn₅Mn₄O₂S₅₈]^12-), T5-MnInOS ([In₃₄Mn₅O₂S₅₈]^8-), and T5-MnInS ([In₂₈Mn₆S₅₄]^12-). Interestingly, transition metals Zn and Mn are successfully introduced into T5-ZnMnInOS and T5-MnInOS via the consolidation of corner-shared Zn₂OS₂ and Mn₂OS₂ units, respectively. Under the photoexcitation of UV light, three compounds can emit bright-orange-red light closely associated with the Mn²⁺ ions, and the compounds containing M₂OS₂ units exhibit better photoluminescence (PL) lifetimes. Variable-temperature PL spectra demonstrate that the introduced M₂OS₂ units are favorable for weakening the deformation of the skeleton structure and decreasing the red shifts of the emission peaks at low temperatures. Moreover, the experimental results exhibit that the three compounds are wide-band-gap semiconductors and that the photogenerated electron separation efficiency can be doubly increased because the intercluster linkers are fixed by the M₂OS₂ units. This work paves a new way for enriching the content and distribution types of transition-metal sites in the supertetrahedral cluster-based metal chalcogenide open frameworks.