Organic–Inorganic Hybrid Materials Based on Basket-like {Ca⊂P₆Mo₁₈O₇₃} Cages

Abstract

Four basket-like organic-inorganic hybrids, formulated as [{Cu(II)(H2O)2}{Ca4(H2O)4(HO0.5)3(en)2}{Ca⊂P6Mo4(V)Mo14(VI)O73}]·7H2O (1), (H4bth)[{Fe(II)(H2O)}{Ca⊂P6Mo18(VI)O73}]·4H2O (2), (H2bih)3[{Cu(II)(H2O)2}{Ca⊂P6Mo2(V)Mo16(VI)O73}]·2H2O (3), (H2bib)3[{Fe(II)(H2O)2}{Ca⊂P6Mo2(V) Mo16(VI)O73}]·4H2O (4), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bib = 1,4-bis(imidazole)butane) have been hydrothermally synthesized and fully characterized. Compounds 1-4 contain polyoxoanion [Ca⊂P6Mon(V)Mo18-n(VI)O73]((6+n)-) (n = 0, 2, or 4) (abbreviated as {P6Mo18O73}) as a basic building block, which is composed of a "basket body" {P2Mo14} unit and a "handle"-liked {P4Mo4} fragment encasing an alkaline-earth metal Ca(2+) cation in the cage. Compound 1 exhibits an infrequent 2D layer structure linked by the Cu(H2O)2 linker and an uncommon tetranuclear calcium complex, while compound 2 is 8-connected 2-D layers connected by binuclear {Fe2(H2O)3} segaments, which are observed for the first time as 2-D basket-like assemblies. Compounds 3 and 4 are similar 1D Z-typed chains bonded by M(H2O)2 units (M = Cu for 3 and Fe for 4). The optical band gaps of 1-4 reveal their semiconductive natures. They exhibit universal highly efficient degradation ability for typical dyes such as methylene blue, methyl orange, and rhodamine B under UV light. The lifetime and catalysis mechanism of the catalysts have been investigated. The compounds also show good bifunctional electrocatalytic behavior for oxidation of amino acids and reduction of NO2(-).

Water-Assisted Synthesis of Molybdenum Disulfide Film with Single Organic Liquid Precursor

“…3(c)). Gaussian curve fitting was used to assign the additional peaks in Mo 3d core level spectra to the Mo 6+ 3d 3/2 and Mo 6+ 3d 5/2 of molybdenum oxide 43 . It is not currently clear why molybdenum oxide formed, but those were eliminated when water was supplied.…”

Modified polyoxometalate: a novel monocapped bi-supporting and reduced α-Keggin structure {PMo12O40[Cu(2,2′-bpy)]}[Cu(2,2′-bpy)(en)(H2O)]2

“…Another unusual feature of compound 1 is the good-quality crystallographic data: (i) all H atoms were located from a difference Fourier Map and refined without any constraints, (ii) the R 1 (0.0188) and wR 2 (0.0456) values are very small, and (iii) all non-H atoms were refined anisotropically and the molecule is well ordered. To our knowledge, such results have been rarely reported for POMs derivatives, especially involving many reduced and heavy atoms (Li et al, 2018;Pang et al, 2015;Zhang et al, 2015b). Therefore, we put forward the possible formation mechanism as shown in Fig.…”

“…However, POM clusters decorated with divalent first-row transition metals as capping atoms, such as Ni 2+ , Ag + and Cu 2+ , have been rarely reported, to our knowledge (Hu et al, 2013;Li et al, 2018;Pang et al, 2015;Yuan et al, 2003). Meanwhile, owing to the Jahn-Teller effect, the Cu 2+ ion possesses flexible coordination geometries and high affinity for O-and N-atom donors, which can easily accommodate the surface coordination environment of POMs and form covalent links between Cu 2+ ions and POMs/ligands (Lan et al, 2008;Wang et al, 2006Wang et al, , 2008Zhang et al, 2015b). Moreover, usually the highly reduced heteropoly molybdenum blues are not stable and inclined to be oxidized in an ambient atmosphere, and are difficult to crystallize from a mixed polyoxoanion solution (Mialane et al, 2002;Zhang et al, 2014Zhang et al, , 2015b.…”

{P2W18O62}-Encapsulated Potassium-Ion Nanotubes Intercalated in Copper Biimidazole Frameworks for Supercapacitors and Hydrogen Peroxide Sensing

“…POMs have shown photocatalytic activity to degrade some organic dyes under UV irradiation. 60 Herein, three classical organic dyesmethylene blue (MB), rhodamine B (RhB), and methyl orange (MO) were chosen as target molecules to estimate the photocatalytic activity of compound 1. The absorption peaks of MB, RhB, and MO are shown in Figure S24 and decrease obviously with increasing reaction time.…”