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Two new metal-chalcogenide-cluster-based frameworks, in which P1-ZnSnS clusters are linked to each other by both corner-shared S2− ions and single metal ions of Zn2+ (or Sb3+) to form one new 3D (3,4)-connected network (MCCF-22) and one 2D-layered framework (MCCF-23), respectively, are reported. Notably, MCCF-22 exhibits good performance toward photodegradation of methylene blue compared with its analogue framework with only S2− ions as the linker. [ABSTRACT FROM AUTHOR]

Incorporating transition metal (TM) complexes into cluster-based chalcogenide frameworks is an effective synthetic strategy to induce structural diversity and control the optoelectronic properties, which may further improve their photocatalytic performance. However, limited studies have been conducted on frameworks constructed by TM complexes covalently bonded with supertetrahedral Tn clusters, let alone on their properties, especially photocatalytic H2 activity. Herein, three new isostructural three-dimensional (3D) neutral inorganic–organic open frameworks of gallium thioantimonate comprised of thiogallate-based supertetrahedral T3 clusters that are covalently bonded with TM complexes ([TM(TEPA)]2+, TM = Mn/Ni/Fe, TEPA = tetraethylenepentamine) at the edges and are linked by single Sb3+ ions at the corner, namely, NCF-3-Mn/Ni/Fe have been solvothermally synthesized and structurally characterized, and display good thermal and chemical stability. Benefiting from an adjustable TM centre, the title compounds possess tunable photocatalytic H2 evolution activity, among which NCF-3-Mn exhibits the highest photocatalytic activity probably due to its favourable band structure and enhanced carrier separation efficiency. [ABSTRACT FROM AUTHOR]

Reported here is the first chiral copper-rich open-framework chalcogenide with a quartz (qtz) topology built on distinctive [Cu5SnSe10] clusters connected by [SnSe4] bridging units. Through in situ sulfur doping, sulfurized compounds could be obtained that exhibit improved photocatalytic performance. This work expands the family of COCs with new building blocks and topologies and demonstrates the significance of chalcogen doping in COCs. [ABSTRACT FROM AUTHOR]

Reported here are three new metal chalcogenide open frameworks built from supertetrahedral [In35S52O8] (denoted as T5-InOS or o-T5) and [In10S20] (denoted as T3-InS) nanoclusters of different sizes and compositions via co-assembly and/or hybrid assembly modes. Such a set of cluster-based superlattices with dia topological structures clearly exhibit quantum size effects and electronic coupling interaction of adjacent nanoclusters, which can effectively explain that the band gap of the T3–(o-T5) hybrid-assembled material lies in the middle of T3–T3 and (o-T5)–(o-T5) co-assembled materials. [ABSTRACT FROM AUTHOR]

Two new metal-chalcogenide-cluster-based frameworks, in which P1-ZnSnS clusters are linked to each other by both corner-shared S 2- ions and single metal ions of Zn 2+ (or Sb 3+ ) to form one new 3D (3,4)-connected network (MCCF-22) and one 2D-layered framework (MCCF-23), respectively, are reported. Notably, MCCF-22 exhibits good performance toward photodegradation of methylene blue compared with its analogue framework with only S 2- ions as the linker.

Incorporating transition metal (TM) complexes into cluster-based chalcogenide frameworks is an effective synthetic strategy to induce structural diversity and control the optoelectronic properties, which may further improve their photocatalytic performance. However, limited studies have been conducted on frameworks constructed by TM complexes covalently bonded with supertetrahedral T n clusters, let alone on their properties, especially photocatalytic H 2 activity. Herein, three new isostructural three-dimensional (3D) neutral inorganic-organic open frameworks of gallium thioantimonate comprised of thiogallate-based supertetrahedral T3 clusters that are covalently bonded with TM complexes ([TM(TEPA)] 2+ , TM = Mn/Ni/Fe, TEPA = tetraethylenepentamine) at the edges and are linked by single Sb 3+ ions at the corner, namely, NCF-3-Mn/Ni/Fe have been solvothermally synthesized and structurally characterized, and display good thermal and chemical stability. Benefiting from an adjustable TM centre, the title compounds possess tunable photocatalytic H 2 evolution activity, among which NCF-3-Mn exhibits the highest photocatalytic activity probably due to its favourable band structure and enhanced carrier separation efficiency.

Reported here is the first chiral copper-rich open-framework chalcogenide with a quartz ( qtz ) topology built on distinctive [Cu 5 SnSe 10 ] clusters connected by [SnSe 4 ] bridging units. Through in situ sulfur doping, sulfurized compounds could be obtained that exhibit improved photocatalytic performance. This work expands the family of COCs with new building blocks and topologies and demonstrates the significance of chalcogen doping in COCs.

Reported here are three new metal chalcogenide open frameworks built from supertetrahedral [In 35 S 52 O 8 ] (denoted as T5-InOS or o-T5) and [In 10 S 20 ] (denoted as T3-InS) nanoclusters of different sizes and compositions via co-assembly and/or hybrid assembly modes. Such a set of cluster-based superlattices with dia topological structures clearly exhibit quantum size effects and electronic coupling interaction of adjacent nanoclusters, which can effectively explain that the band gap of the T3-(o-T5) hybrid-assembled material lies in the middle of T3-T3 and (o-T5)-(o-T5) co-assembled materials.