Syntheses and Characterizations of Three Low-Dimensional Chloride-Rich Zincophosphates Assembled about [d-Co(en)₃]³⁺and [dl-Co(en)₃]³⁺Complex Cations

Abstract

Three new chloride-rich zincophosphates including two zero-dimensional (0D) clusters [dl-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8] (denoted ZnPO-CJ33) and [d-Co(en)3]2[Zn4(H2PO4)2(HPO4)2Cl8] (denoted ZnPO-CJ34), and one-dimensional (1D) zincophosphate chain [dl-Co(en)3][Zn2(H2PO4)(HPO4)2Cl2] (denoted ZnPO-CJ35) have been solvothermally prepared. ZnPO-CJ33 and ZnPO-CJ34 possess the same cluster structure as the macroanionic [Zn4H6P4O16Cl8]6- unit formed by alternation of ZnOCl3/ZnO3Cl and HPO4/H2PO4 tetrahedra but differ in the countercations. The racemic [dl-Co(en)3]3+ cations are located among the clusters of ZnPO-CJ33, whereas chiral [d-Co(en)3]3+ cations are located among the clusters of ZnPO-CJ34. ZnPO-CJ34 templated by the optically pure chiral [d-Co(en)3]3+ cations is the first chiral monomeric zincophosphate. ZnPO-CJ35 templated by the racemic [dl-Co(en)3]3+ cations possesses a 1D infinite chain structure formed by the alternation of ZnO3Cl and HPO4/H2PO4 tetrahedra. The 1D chain structure of ZnPO-CJ35 can also be viewed as generated from the condensation of 0D clusters of ZnPO-CJ33, with the terminal Cl ions replaced by HPO4 groups. Experimentally, the structural transformation from ZnPO-CJ33 to ZnPO-CJ35 has been investigated.

New Framework Iodoargentates: M(en)3Ag2I4 (M = Zn, Ni) with Tridymite Topology

“…Recently, the reaction between silver iodide and iodide ions attracted our attention because the solubility of AgI increases in appropriate solvents upon the addition of excess KI and the active intermediate AgI 2 − anion is a good precursor to construct higher dimension compounds. Significantly, the introduction of the metal complexes as templates instead of organic amines has proven to be an effective route to generating open-framework architectures . Here we report two new framework complexes, 1 and 2 , which represent the first framework iodoargentates.…”

Facile synthesis, microstructure and photophysical properties of core-shell nanostructured (SiCN)/BN nanocomposites

“…This reaction was performed in a purified argon atmosphere via the standard Schlenk technology2252. In addition, the [Co(en) 3 ]·Cl 3 complex was synthesized by CoCl 2 (Aldrich) and ethylenediamine (Aldrich), as described previously60.…”

Hydrothermal Synthesis of New Organically Templated Beryllium Phosphite and Phosphate with 3,4‐connected Networks

“…Of these, metal phosphates have evidenced extraordinary expansion in terms of the structural and compositional diversities 8. A very wide range of transition metals and main group elements have been incorporated into the frameworks of these materials, in which some typical examples include Zn 3 (PO 4 ) 2 (PO 3 OH)(H 2 DACH) · 2H 2 O (denoted as ND‐1) with extra‐large 24‐ring channels,9 H 3 N(CH 2 ) 6 NH 3 · Zn 4 (PO 4 ) 2 · Zn 4 (HPO 4 ) 2 · 3H 2 O and [H 2 CHBMA][Zn 2.5 (PO 4 )(HPO 3 ) 2 ] · H 2 O (denoted as TJPU‐3) with 20‐ring channels,10,11 as well as several cases with helical channels or chiral frameworks 12–14. Using pseudo‐pyramidal phosphite [HPO 3 2– ] groups to substitute tetrahedral [PO 4 3– ] units in metal phosphate architectures recently has resulted in a new class of metal phosphites with great success.…”