Assembly of Organic–Inorganic Hybrid Supramolecular Materials Based on Basketlike {M⊂P6Mo18O73} (M = Ca, Sr, Ba) Cage and Transition-Metal Complex

et al. 2015

Dalton Trans.

Self Cite

A series of basket-like heteropoly blues, formulated as (H4bth)[{Cu(H2O)}2{Sr ⊂ P6MoV2MoVI16O73}]·4H2O (1), {H2bih}3[{FeII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (2), (H2bih)3[{CoII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (3), (H2bih)3[{NiII(H2O)2}{Sr ⊂ P6MoV2MoVI16O73}]·2H2O (4), (H2bih)2(H2bip)[{Zn (H2O)0.5}{Sr ⊂ P6MoV2MoVI16O73}]·5.5H2O (5), (bth = 1,6-bis(triazole)hexane; bih = 1,6-bis(imidazol)hexane; bip = 1,5-bis(imidazol)pentane) have been synthesized hydrothermally and fully characterized. The structural analysis shows that all the compounds contain two electron reduced polyanions [Sr ⊂ P6MoV2MoVI16O73]8− (abbreviated as {P6Mo18O73}), which consists of a tetra vacant γ-Dawson-type{P2Mo14} unit and a “handle”-shaped {P4Mo4} segment encapsulating a Sr2+ cation in the central cavity. Compound 1 is a 6-connected two-dimensional (2D) layer, which represents the first 2D assembly of basket-type polyoxometalates. Compounds 2–4 are isostructural one-dimensional zigzag chains linked by an M(H2O)2 linker (M = iron for 2, cobalt for 3, and nickel for 4). Compound 5 is a dimeric cluster supported by a binuclear {Zn2(H2O)} unit. The optical band gaps of 1–5 reveal their semiconductive natures. The compounds if used as photocatalysts exhibit a universal high efficiency degradation ability for dyes such as methylene blue, Rhodamine B, and Azon phloxine. The lifetime and reaction mechanism of the catalysts were investigated with a series of experiments. The compounds also show good bifunctional electrocatalytic behavior for the oxidation of ascorbic acid (AA) and reduction of nitrite ions.

Section: Synthesismentioning

confidence: 99%

Assembly of a basket-like {Sr ⊂ P₆Mo₁₈O₇₃} cage from 0D dimmer to 2D network and its photo-/electro-catalytic properties

et al. 2015

Dalton Trans.

Self Cite

“…It is proved that the space size of the basket-like cluster tended to capture larger alkali metals or alkaline earth cations. 15,17 In fact, the incorporation of the large cations can also stabilize the basket-like cage.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

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

et al. 2015

Inorg. Chem.

Self Cite

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(-).

“…15,17,18 In addition, two key factors affect the formation of the resulting products: one is the organic ligand, and the other is the kind of molybdenum source. 15,17,18 In addition, two key factors affect the formation of the resulting products: one is the organic ligand, and the other is the kind of molybdenum source.…”

Section: Synthesismentioning

confidence: 99%

1,4-Bis(imidazole)butane ligand and strontium(ii) directed 1-D chains based on basket-type molybdophosphates and transition metal (TM) linkers

et al. 2015

CrystEngComm

Self Cite

Five unclassical heteropoly blues, ĲH 2 bib) 3 ĳ{TM II ĲH 2 O) 2 }{Sr⊂P 6 Mo 2 V Mo 16 VI O 73 }]·nH 2 O (TM = Fe (1), Co (2), Ni (3), Cu (4), Zn (5)); bib = 1,4-bisĲimidazole)butane), have been hydrothermally synthesized and fully characterized. Compounds 1-5 are based on the basket-shaped ĳSr⊂P 6 Mo 2 V Mo 16 VI O 73 ] 8− (abbreviated as {P 6 Mo 18 O 73 }) units, which consist of a vacant Dawson-type "basket body" {P 2 Mo 14 } unit and a "handle"-like {P 4 Mo 4 } fragment encasing a Sr 2+ cation in the central cage. All the compounds exhibit isostructural 1-D zigzag chains linked by a {TMĲH 2 O) 2 } unit, which are observed for the first time as 1-D basket-like assemblies connected by a TM linker. The optical band gaps of 1-5 show that they are semiconductor materials and potential photocatalysts. Compound 2 as a representative catalyst exhibits a universal highly efficient degradation ability for typical dyes MB, MO, and RhB under UV light and bifunctional electrocatalytic behavior for oxidation of AA and reduction of NO 2 − . V Mo 15 VI O 73 ], was reported by Zhang in 2004. 14 Then, two organic-inorganic hybrids CrystEngComm This journal is