Dongying Shi

Four types of 1D or 2D organic–inorganic hybrids assembled by arsenotungstates and CuII–LnIII/IV heterometals

Four types of organic–inorganic hybrids Na[Cu(en)2(H2O)]4[Cu(en)2]2[Cu(H2O)4]0.5{Cu(en)2[H2CeIV(α-AsW11O39)2]2}·10H2O (1), Na3[Cu(en)2(H2O)][Cu(en)2]1.5[H3Ln(α-AsW11O39)2]·xH2O [Ln = PrIII, x = 5 (2); Ln = NdIII, x = 4.5 (3); Ln = SmIII, x = 5.5 (4); Ln = EuIII, x = 4 (5); Ln = TbIII, x = 4 (6)], [Cu(dap)(H2O)2]0.5[Cu(dap)2(H2O)]2[Cu(dap)2]3[Ln(α-AsW11O39)2]·xH2O [Ln = PrIII, x = 3 (7); Ln = EuIII, x = 3 (8)] and [Cu(dap)2]5.5[Ln(α-AsW11O39)2]·xH2O [Ln = TbIII, x = 6 (9); Ln = DyIII, x = 5 (10)] (en = ethylenediamine, dap = 1,2-diaminopropane) have been hydrothermally synthesized and fully characterized by elemental analyses, IR spectra, solid-state UV spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1 exhibits the first 2D TM–Ln heterometallic sheet architecture with a 4-connected topology established by tetrameric [Cu(H2O)4{Cu(en)2[H2Ce(α-AsW11O39)2]2}2]26− units via [Cu(en)2]2+ bridges. 2–6 are isomorphic and display the unique 2D (6,3)-network topology constructed from 1 : 2-type [H3Ln(α-AsW11O39)2]8− units through [Cu(en)2]2+ linkers. 7–8 represent the first 1D “dendritic” chain-like TM–Ln heterometallic POMs based on the 1 : 2-type [Ln(α-AsW11O39)2]11− units. 9–10 are the unique 2D sheets built by 1 : 2-type [Ln(α-AsW11O39)2]11− units and [Cu(dap)2]2+ connectors, in which the [Ln(α-AsW11O39)2]11− subunits act as 5-connected nodes and adjacent 2D sheets are packed in the mode of –AAA–. The photocatalytic measurements show that 1–10 can to some extent inhibit the photodegradation of rhodamine-B (RhB). Moreover, the luminescence properties of 5–6 and 8–9 have been investigated.

Two 1-D multi-nickel substituted arsenotungstate aggregates

Two multi-nickel substituted arsenotungstate aggregates [enH2]2[Ni(H2O)4]2[Ni(en)2]2[Ni(en)]2{[(α-AsW6O26)Ni6(OH)2(H2O)3(en)(B-α-AsW9O34)]2[W4O16][Ni3(H2O)2(en)]2}·16H2O (1) and [Ni(H2O)(en)2]2[Ni(H2O)3(en)][Ni(H2O)(en)]{[(α-AsW6O26)Ni6(OH)2(en)2.5(B-α-AsW9O34)]2H4[W4O16][Ni4(H2O)2(en)2]2}·13H2O (2) (en = ethylenediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. 1 is a 1D chain architecture built by eighteen NiII substituted {[(α-AsW6O26)Ni6(OH)2(H2O)3(en)(B-α-AsW9O34)]2[W4O16][Ni3(H2O)2(en)]2}16− units via two [Ni(H2O)4]2+ and two [Ni(en)2]2+ bridges. 2 also displays a 1D chain motif constructed from twenty NiII substituted {[(α-AsW6O26)Ni6(OH)2(en)2.5(B-α-AsW9O34)]2H4[W4O16][Ni4(H2O)2(en)2]2}8− units via single en bridges. Notably, 1 and 2 not only represent rare eighteen/twenty NiII substituted arsenotungstates, but also display an unusual construction motif simultaneously containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− fragments. Magnetic measurements demonstrate that 1 and 2 indicate the ferromagnetic couplings within NiII centers.

Two organic–inorganic hybrid 1-D and 3-D polyoxotungstates constructed from hexa-CuII substituted sandwich-type arsenotungstate units

Two organic–inorganic hybrid hexa-CuII substituted sandwich-type arsenotungstates [Cu(en)2(H2O)]2 [Cu(en)2][Cu6(en)2(H2O)2(B-α-AsW9O34)2]·en·9H2O (1) and [Cu(dap)2]3[Cu6(dap)2(H2O)2(B-α-AsW9O34)2]·4H2O (2) (en = ethylenediamine, dap = 1,2-diaminopropane) have been hydrothermally prepared and structurally characterized by elemental analysis, IR spectra, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 is an organic–inorganic hybrid 1-D chain constructed from hexa-CuII substituted [Cu6(en)2(H2O)2(B-α-AsW9O34)2]6− sandwich-type units and [Cu(en)2]2+ linkers whereas 2 shows the six-connected 3-D extended framework built by hexa-CuII sandwiched [Cu6(dap)2(H2O)2(B-α-AsW9O34)2]6− units and [Cu(dap)2]2+ connectors. To our knowledge, 1 and 2 represent the first organic–inorganic hybrid high-dimensional arsenotungstates containing hexa-CuII sandwiched polyoxometalate units. The results of magnetic susceptibility measurements demonstrate that 1 and 2 indicates the ferromagnetic couplings within CuII centers. The photocatalytic measurements illustrate that 1 and 2 can to some extent inhibit the photodegradation of rhodamine-B (RhB).

Two 3d–4f heterometallic monovacant Keggin phosphotungstate derivatives

Two 3d–4f heterometallic monovacant Keggin phosphotungstate derivatives [Cu(dap)(H2O)2]0.5[Cu(dap)2]4H2[Pr(α-PW11O39)2] · 3H2O (1) and [Cu(en)2(H2O)]2[Cu(en)2]1.5H4[Pr(α-PW11O39)2] · 10H2O (2) (dap = 1,2-diaminopropane, en = ethylenediamine) have been hydrothermally synthesized by reaction of the trivacant Keggin phosphotungstate precursor Na9[A-α-PW9O34] · 7H2O with CuCl2 · 2H2O and PrCl3 in the presence of dap or en and structurally characterized by elemental analyses, IR spectra, X-ray single-crystal diffraction, and thermogravimetric analyses. Compound 1 crystallizes in the triclinic space group P 1 with a = 17.325(3), b = 18.917(3), c = 19.938(3) Å, α = 104.481(2), β = 98.968(3), γ = 91.306(3)°, V = 6236.4(18) Å3, Z = 2, GOOF = 1.000, R 1 = 0.0806, wR 2 = 0.2016. Compound 2 also belongs to the triclinic space group P 1 with a = 16.005(4), b = 18.053(4), c = 21.127(5) Å, α = 113.894(3), β = 90.745(4), γ = 94.255(4)°, V = 5560(2) Å3, Z = 2, GOOF = 0.999, R 1 = 0.0686, wR 2 = 0.1885. Both 1 and 2 display organic–inorganic hybrid 2-D sheet architectures built by classic mono-PrIII sandwiched dimeric moieties [Pr(α-PW11O39)2]11− through [Cu(L)2]2+ bridges (L = dap, en), which represent rare organic–inorganic hybrid 2-D 3d–4f heterometallic monovacant Keggin polyoxometalates.

Hydrothermal syntheses and structural characterization of two sandwich-type arsenotungstates

Two new organic–inorganic composite sandwich-type arsenotungstates [H2dap]6H8[Ni4(H2O)2(B-α-AsW9O34)2]2 · 33H2O (1) and {[Ni(dap)2(H2O)]2[Ni(dap)2]2[Ni4(Hdap)2(B-α-AsW9O34)2]} · 4H2O (2) (dap = 1,2-diaminopropane) have been hydrothermally synthesized by reaction of Na8[A-α-HAsW9O34] · 11H2O with NiCl2 · 6H2O in the presence of 1,2-diaminopropane and characterized by elemental analysis, IR spectra, X-ray single-crystal diffraction, and thermogravimetric analysis. 1 crystallizes in the triclinic P 1 space group with a = 16.351(6) Å, b = 16.423(6) Å, c = 19.894(7) Å, α = 110.630(6)°, β = 92.684(7)°, γ =104.946(7)°, V = 4774(3) Å3, Z = 1, GOOF = 1.033, R 1 = 0.0517, wR 2 = 0.1086. 2 also crystallizes in the triclinic P 1 space group with a = 13.305(4) Å, b = 13.882(4) Å, c = 17.031(5) Å, α = 68.109(5)°, β = 71.511(4)°, γ = 88.407(5)°, V = 2753.5(14) Å3, Z = 1, GOOF = 1.051, R 1 = 0.0491, wR 2 = 0.1150. Notably, 1 is a discrete structure, composed of two tetra-NiII substituted sandwich-type polyoxoanions [Ni4(H2O)2(B-α-AsW9O34)2]10− with different spatial orientation, whereas 2 displays a organic–inorganic composite 2-D sheet architecture constructed by tetra-NiII sandwiched [Ni4(H2O)2(B-α-AsW9O34)2]10− units by means of [Ni(dap)2]2+ bridges. Some previously reported transition-metal-substituted sandwich-type polyoxotungstates have been summarized.

A novel 2D phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O constructed from strandberg-type polyoxometalate units and copper-organic cation bridges

A 2D Strandberg-type phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O (I) (En = ethylenediamine) has been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. The molecular structural unit of I consists of one Strandberg-type [P2Mo5O23]6− subunit, two [Cu(En)(EnH)]3+ cations and three lattice water molecules. The most remarkable feature of I is that each molecular structural unit is connected with adjacent four same units by four [Cu(En)(EnH)]3+ bridges constructing the 2D organic-inorganic hybrid sheet structure with a 4-connected topology. As far as we know, such 2D hybrid sheet structure constructed from Strandberg-type phosphomolybdate units and copper-organic cation bridges is very rare.

A 2-D Organic–Inorganic Hybrid Copper-Yttrium Heterometallic Monovacant Keggin Phosphotungstate Derivative: [Cu(dap)2]5.5[Y(α-PW11O39)2]·4H2O

A novel 2-D organic–inorganic hybrid copper-yttrium heterometallic monovacant Keggin phosphotungstate derivative [Cu(dap)2]5.5[Y(α-PW11O39)2]·4H2O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized by reaction of Na9[A-α-PW9O34]·7H2O, CuCl2·2H2O, YCl3 and dap and structurally characterized by elemental analysis, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), and X-ray single-crystal diffraction. 1 illustrates an interesting 2-D copper-yttrium heterometallic sheet architecture with a 5-connected topology built by 1:2-type [Y(α-PW11O39)2]11− subunits and [Cu(dap)2]2+ bridges. To our knowledge, 1 represents a rare 2-D organic–inorganic hybrid Keggin phosphotungstate-based transition metal and rare-earth heterometallic derivative. The photocatalytic measurements show that 1 can inhibit the photodegradation of rhodamine-B.

Synthesis, structure, and photoluminescence properties of a novel 3D 3d-4f heterometallic polymer: Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (H2Bpdc = 2,2′-bipyridyl-5,5-dicarboxylic acid)

A novel 3D 3d–4f heterometallic polymer Pr4(H2O)9Cu3.5Cl0.5(Bpdc)6.5(OH)2 · 5H2O (I) (H2Bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) has been hydrothermally synthesized by the reaction of CuCl2 · 2H2O, PrCl3, H2Bpdc, TAA (TAA = 1H-tetrazolyl-1-acetic acid) and glacial acetic acid and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting heterometallic 3D coordination framework constructed from 2D praseodymium-oxygen layers and [Cu(Bpdc)2]3− and [CuCl(Bpdc)]2− pillars. The photofluorescence properties of I have been investigated.

A novel 2D organic-inorganic hybrid 3d–4f polyoxometalate built by [Gd(α-PW11O39)2]11− units and [Cu(Dap)2]2+ bridges

A novel 2D organic-inorganic hybrid 3d–4f polyoxometalate [Cu(Dap)2(H2O)][Cu(Dap)2]4.5[Gd(α-PW11O39)2] · 5H2O (I) (Dap = 1,2-diaminopropane) built by [Gd(α-PW11O39)2]11− units and [Cu(Dap)2]2+ bridges has been synthesized hydrothermally by the reaction of GdCl3, CuCl2 · 2H2O, Na9[A-α-PW9O34] · 7H2O, and Dap and characterized by elemental analysis, IR spectrum, UV spectrum, powder X-ray diffraction, and single-crystal X-ray diffraction. Single-crystal structural analysis shows that I displays an interesting 2D 3d–4f heterometallic sheet architecture with a 5-connected topology constructed from 1: 2-type [Gd(α-PW11O39)2]11− subunits and [Cu(Dap)2]2+ bridges. To the best of our knowledge, I represents a rare organic-inorganic hybrid 2D 3d–4f heterometallic monovacant Keggin phosphotungstate.

A 2D organic-inorganic hybrid [Cu(En)2(H2O)]2[Cu(En)2]4[Si2Cu2W22O78]·7H2O assembled from monocopper(II)-substituted Keggin silicotungstate dimers

The reaction of Na10[A-α-SiW9O34] · 18H2O with CuCl2 · 2H2O in the participation of ethylenediamine (En) under hydrothermal conditions resulted in a 2D organic-inorganic hybrid monocopper(II)-substituted Keggin silicotungstate [Cu(En)2(H2O)]2[Cu(En)2]4[Si2Cu2W22O78] · 7H2O (I), which was structurally characterized by elemental analyses, IR spectrum, UV spectrum, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Single crystal structural analysis shows that adjacent monocopper(II)-substituted Keggin silicotungstate [Si2Cu2W22O78]12− dimeric subunits are interconnected by sharing terminal oxygen atoms to make the 1D polymeric linear chain and neighboring chains are combined with each other through [Cu(En)2]2+ connectors giving rise to an interesting 2D organic-inorganic hybrid sheet architecture with a 4-connected topology. To our knowledge, I is the rare organic-inorganic hybrid 2D polyoxometate constructed by mono-transition-metal substituted Keggin silicotungstate dimeric subunits. The photocatalytic measurement illustrates that I can to some extent inhibit the photodegradation of rhodamine-B.