Two new metal-chalcogenide-cluster-based frameworks with single metal ions of Zn²⁺(/Sb³⁺) serving as inter-cluster linkers

Abstract

Reported here are two new metal-chalcogenide-cluster-based frameworks, in which P1-ZnSnS clusters are linked each other by both corner-shared S2- ion and single metal ion of Zn2+ (or Sb3+) to form...

M–Sn–Q (M = Zn, Cd; Q = S, Se) Compounds Templated by (Alkyl)ammonium Species: Synthesis, Crystal Structure, and Sr2+ Adsorption Property

“…This linkage fashion contributes to a T d -symmetrically supertetrahedral structure (denoted as P1 type according to the literature , ) with terminal S···S edges of 10.11 Å. P1 clusters were also observed in other group 12/16, − 13/16, ,− and 12/14/16 ,, sulfides or selenides. The [Zn 4 Sn 4 S 17 ] 10– cluster in this work possesses four terminal S 2– ions that show great potentials for interconnection through sharing the common S 2– or binding other bridging metal ions/clusters. ,, …”

“…This assembly contains four irregular 32-MR windows of {Zn 8 Sn 8 Se 16 } with an approximate diameter of 20.70 × 9.36 Å 2 (Figure S11). To the best of our knowledge, the {Zn­(H 2 O)} 2+ group was scarcely reported in the construction of Zn–Sn–Se frameworks, and the only related sulfide analogue is MCCF-22 whose framework is built up by P1-[Zn 4 Sn 4 S 17 ] 10– clusters and {Zn­(H 2 O)} 2+ units . The extra-framework space in 3 is occupied by highly disordered [CH 3 CH 2 NH 3 ] + cations and water molecules, and the cation/solvent-accessible volume fraction is calculated to be approximately 57.7% according to the program PLATON …”

“…To the best of our knowledge, the {Zn(H 2 O)} 2+ group was scarcely reported in the construction of Zn−Sn−Se frameworks, and the only related sulfide analogue is MCCF-22 whose framework is built up by P1-[Zn 4 Sn 4 S 17 ] 10− clusters and {Zn(H 2 O)} 2+ units. 39 The extra-framework space in 3 is occupied by highly disordered [CH 3 CH 2 NH 3 ] + cations and water molecules, and the cation/solvent-accessible volume fraction is calculated to be approximately 57.7% according to the program PLATON. 76 It would give better structural understanding to investigate the topologies of the microporous frameworks in 2 and 3. , 54 are also listed here for comparison (Figure 6).…”

“…Ammonium and alkylammonium, on the other hand, are regarded as effective structure-directing agents (SDAs) for inorganic materials owing to their flexibility and tunability in molecular size and conformation . For the preparation of Zn/Cd–Sn–Q compounds, polyamine (e.g., 1,2-diaminopropane, , ethylenediamine) and large amine (e.g., 1,5-diazabicyclo[4.3.0]­non-5-ene, N -aminoethylpiperazine , ) molecules have been recently used as the SDAs for constructing incompact stackings of chains/layers or highly porous frameworks. By contrast, ammonium and small alkylammonium species (e.g., methylammonium, dimethylammonium, and ethylammonium) are rarely explored for this synthetic purpose, as evidenced by the limited examples including [(Me) 2 NH 2 ] 2 ZnSn 3 Se 8 , and [CH 3 NH 3 ] 3 [NH 4 ] 3 Cd 4 Sn 3 Se 13 ·3H 2 O .…”

A Heniconuclear {Mn21} Cluster-Based Coordination Polymer with Manganese(II) Linkers Showing High Proton Conductivity

“…However, TM-linked Mn-based CCPs from aqueous solution are uncommonly sparse, given their green-synthesis nature and intrinsic water stability. Additionally, not only can TM linkers significantly affect the configuration of the frame structure, but they can also bring about desirable properties, including catalytic activity, photoluminescence, and magnetic behavior, to name a few. − …”