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A novel two-dimensional (2-D) solid material [Ni(en)2]2{SiMoVI8VIV6O42[Ni(en)2]2}·4H2O 1 (en = ethylenediamine) has been hydrothermally synthesized and structurally characterized by IR, UV–Vis spectrum, elemental analysis, XRD, ESR, XPS, X-ray diffraction analysis, magnetic property analysis and electrochemistry study. Single-crystal X-ray analysis reveals that the 2-D framework of compound 1 is based on Mo/V/Si bicapped Keggin clusters interconnected by nickel ethylenediamine complexes. Magnetic susceptibility measurement indicates that compound 1 exhibits antiferromagnetic coupling interactions.

Three compounds, [AsMo8V6O42][Cu(2,2ʹ-bpy)2]2[Cu(2,2ʹ-bpy)]·4H2O (1), [PMo8V6O42][Cu(2,2ʹ-bpy)2]2[Cu(2,2ʹ-bpy)]·3H2O (2) and [PMo8V6O42][Cu(2,2ʹ-bpy)2]2[Cu(2,2ʹ-bpy)]·3.5H2O (3), have been synthesized under hydrothermal conditions and characterized by IR, UV–vis, XRD, TG, elemental analysis, and X-ray diffraction analysis. Single-crystal X-ray structure analysis reveals that 1 and 2 are isostructural and isomorphous, whereas 2 and 3 are polymorphs. Polymorphs of 1 have not been synthesized yet. The mixed-valent transition metal ion in 1–3 has been further confirmed by TG analyses. Catalytic properties of 1 and 2 have also been studied.

Two new compounds, [Ni(en)2]{[Ni(en)2]2[MoVI 6MoV 2VIV 8O40(SiO4)]}[(NH2)2(C2H4)2NH]·2H2O(1) and [Ni(en)2]{[Ni(en)2]2[MoVI 5MoV 3VIV 8O40(VO4)]}(en)·H2O(2)(en=ethylenediamine), have been hydrothermally synthesized and characterized by elemental analysis, infrared(IR), X-ray photoelectron spectroscopy(XPS), electron spin-resonance(ESR) and thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD) analysis. Both the compounds exhibit a 1D chain composed of bi-supporting tetra-capped Keggin clusters and nickle coordination fragments. The 1D chains are further assembled into a 3D supramolecular network with different packing modes via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of antiferromagnetic interactions.

A new compound, [Cu(en)2(H2O)]{[Cu0.5(en)]3[VVW6.5VIW3VV4.5IVO42Cu(en)2]}·3.5H2O (1) (en = ethylenediamine), has been hydrothermally synthesized and characterized by elemental analysis, IR, ESR, XPS, TG analysis and single-crystal X-ray diffraction analysis. Compound 1 exhibits a novel 2-D structure linked by 1-D infinite left- and right-handed helical chains and transition metal coordination fragments. Adjacent layers are further interconnected into a 3-D supramolecular structure via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrated the presence of antiferromagnetic interactions.

A new compound, [Cu(en) 2 ][Cu(en) 2 (H 2 O)] 2 [SiMo 8 V 6 O 42 ][Cu(en) 2 ]·1.5H 2 O ( 1 ) (en = ethylenediamine), has been hydrothermally synthesized and characterized by elemental analysis, IR, ESR spectrum, TG analysis and single-crystal X-ray diffraction analysis. Compound 1 represents a 1-D zigzag chain-like structure constructed from dimeric units of bi-capped polyoxoanions {[Cu(en) 2 ] 2 [Cu(en) 2 (H 2 O)] 2 [SiMo 8 V 6 O 42 ] 2 [Cu(en) 2 ]} 6− and transition metal coordination fragment [Cu(en) 2 ] 2 + . The adjacent chains are further interconnected into a 3-D supramolecular structure via hydrogen bonds. The magnetic susceptibility of 1 demonstrated the presence of antiferromagnetic interactions.

Four new hybrid compounds based on Keggin polyoxometallates and transition metal complexes, [Cu(phen)2]4[GeW12O40] (1), [Cu(bpy)(phen)]2[Cu(bpy)2]3[BW12O40] (2), [Cu(bpy)(phen)][Cu(bpy)2]3[SiW12O40] (3) and [Cu(bpy)2]4[GeW12O40] (4) (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine), have been hydrothermally synthesized and characterized by IR spectra, UV–Vis, XPS, XRD and single crystal X-ray diffraction analyses. Compounds 1, 2, 3 and 4 are new examples of hybrids based on polyoxometallates and transition metal complexes with a lower positive charge.

Two new compounds, namely [Cu 4 (4,4′-bpy) 4 ][SiW 12 O 40 ]·6H 2 O ( 1 ) and [Cu 2 (4,4′-bpy) 2 ][SiMo 12 O 40 ]·(H 2 4,4′-bpy) ( 2 ) (bpy = bipyridine), have been hydrothermally synthesized and characterized by IR, UV–Vis, X-ray photoelectron spectroscopy (XPS), powder XRD, elemental analyses and single crystal X-ray diffraction. The two compounds represent new examples of compounds constructed from Keggin polyanions, metal ions and organic ligands. Compounds 1 and 2 both contains Cu(4,4′-bpy) n n+ infinite chains and [SiM 12 O 40 ] 4− anions (M = W for 1 and M = Mo for 2 ). However, the structures of compounds 1 and 2 are thoroughly different. The Cu(4,4′-bpy) n n+ infinite chains and [SiW 12 O 40 ] 4− anions in compound 1 are connected into a 2-D layered framework structure, and the Cu(4,4′-bpy) n n+ infinite chains and [SiMo 12 O 40 ] 4− anions in compound 2 are linked into a 1-D ladder-like structure.

Two new compounds [Cu(enMe) 2 ][Cu(enMe) 2 (H 2 O)][SiMo V 6 Mo VI 6 Sb 2 O 40 ] ( 1 ) and [Ni(en) 2 ] 2 [SiMo V 6 Mo VI 6 Sb 2 O 40 ] ( 2 ) (enMe = 1,2-diaminopropane, en = 1,2-ethylenediamine) have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, elemental analyses and single crystal X-ray diffraction. The two compounds represent the first examples of hybrids based on bi-antimony capped Keggin polyanions {SiMo 12 Sb 2 O 40 } and different transition metal coordination complexes.

Two supramolecular compounds based on Keggin-type polyoxometalates (POMs), (4,4′-H2bpy)(4,4′-Hbpy)[PMo12O40] (1) and (4,4′-H2bpy)(4,4′-Hbpy)2[SiW12O40] · 4H2O (2), have been synthesized hydrothermally and characterized by elemental analyses, IR, UV-Vis, XPS spectra, thermogravimetric analyses, and single-crystal X-ray diffraction analyses. The two compounds consist of 4,4′-bipyridine (4,4′-bpy) ligands and different Keggin-type POMs which are [PMo12O40]3− for 1 and [SiW12O40]4− for 2. There are hydrogen-bonding interactions between the POMs, 4,4′-bipyridine, and/or water in 1 and 2. In addition, 2 contains an uncommon (H2O)2 water cluster.

Four new organic–inorganic hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}: [H24,4′-bpy][PMo12Sb2O40]·6H2O (1), [Him]2[PMo12Sb2O40]·H2O (2), [H3(DABCO)2][PMo12Sb2O40]·2H2O (3) and [Mn(phen)3][PMo12Sb2O40] (4) (bpy = bipyridine, im = imidazole, DABCO = 1,4-diazabicyclo[2,2,2]octane, phen = phenanthroline) have been prepared hydrothermally and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, elemental analyses, fluorescence analysis and single crystal X-ray diffraction analyses. The four compounds are new examples of hybrid compounds based on bicapped Keggin polyoxometalate {PMo12Sb2O40}. Compound 1, 2 and 3 are constructed from {PMo12Sb2O40} anions and different organic moieties, respectively. Compound 4 is formed by combining {PMo12Sb2O40} anions and manganese coordination complexes.

Based on the hydrothermal in situ acylation reaction of 4,4′-biphthalic acid (bpha) with N2H4·H2O, a new acylhydrazidate-bridged 1-D chained Cd2+ coordination polymer [Cd(BPTH)(phen)]·3.75H2O (BPTH = 4,4′-biphthalhydrazidate, phen = phenanthroline) was synthesized, and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction (XRD), thermogravimetric analysis and single-crystal XRD. With ancillary phen molecules, the BPTH molecules link the Cd2+ centers into a 1-D staircase chain structure of compound 1 based on the Cd2O2 clusters. Based on the hydrothermal in situ acylation reaction of 4,4′-biphthalic acid (bpha) with N2H4·H2O, a new acylhydrazidate-bridged 1-D chained Cd2+ coordination polymer [Cd(BPTH)(phen)]·3.75H2O (BPTH = 4,4′-biphthalhydrazidate, phen = phenanthroline) was synthesized. With ancillary phen molecules, the BPTH molecules link the Cd2+ centers into a 1-D staircase chain structure of compound 1 based on the Cd2O2 clusters.

Two types of organic cyclic aliphatic diamine molecules piperazine (pip) and 1,3-bis(4-piperidyl)propane (bpp) were used, respectively, to react with an inorganic mixture of CuI and KI in the acidic CH{sub 3}OH solutions under the solvothermal conditions, generating finally three new organically templated iodocuprates as 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 (tmpip=N,N,N',N'-tetramethylpiperazinium) and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Note that the templating agent tmpip{sup 2+} in compound 2 originated from the in situ N-alkylation reaction between the pip molecule and the methanol solvent. The photoluminescence analysis indicates that the title compounds emit the different lights: yellow for 1, blue for 2 and yellow-green for 3, respectively. - Graphical abstract: The solvothermal self-assemblies of CuI, KI and pip/bpp in acidic CH{sub 3}OH solutions created three iodocuprates 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Highlights: > A new layered iodocuprate(I) with 20-membered rings was hydrothermally prepared. > A simple approach to prepare the new organic templating agent was reported. > Photoluminescence analysis indicates the emission for iodocuprate(I) is associated with the Cu...Cu interactions.

The hydrothermal self-assemblies of Pb{sup 2+}/Cd{sup 2+} salt, 4,5-dichlorophthalic acid (dcpha), N{sub 2}H{sub 4}.H{sub 2}O together with 1,10-phenanthroline.H{sub 2}O (phen) or 2,2'-bipyridine (bpy) generated two new monoacylhydrazidate-bridged 1-D chained coordination polymers [Pb{sub 2}(DCPTH){sub 4}(phen){sub 2}] 1 and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] 2 (DCPTH=4,5-dichlorophthalhydrazidate, dcph=4,5-dichlorophthalate). The monoacylhydrazidate ligand DCPTH originated from the hydrothermal in situ acylation reaction between dcpha and N{sub 2}H{sub 4}.H{sub 2}O. In compound 1, two types of coordination modes for DCPTH are found, which link alternately the Pb(II) centers into a 1-D chain structure of compound 1 with ancillary phen molecules. In compound 2, DCPTH and dcph as the mixed bridges extend the Cd(II) centers into a 1-D chain structure of compound 2 with auxiliary bpy molecules. DCPTH in compound 2 shows a different coordination mode from those observed in compound 1. -- Graphical abstract: By applying the in situ acylation reaction between 4,5-diclorophthalic acid and N{sub 2}H{sub 4}.H{sub 2}O, two 4,5-dichlorophthalhydrazidate-bridged chained compounds [Pb{sub 2}(DCPTH){sub 4}(phen){sub 2}] and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] (4,5-dichlorophthalhydrazidate=DCPTH, and dcph=4,5-dichlorophthalate) were hydrothermally synthesized. Display Omitted Research highlights: > In this article, we first reported the preparations and structural characterization of two examples of 4,5-dichlorophthalhydrazidate-bridged chained coordination polymers [Pb{sub 2}(DCPTH){sub 4}(phen){submore » 2}] 1 and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] 2. 4,5-dichlorophthalhydrazidate derived from the hydrothermal in situ acylation reactions between 4,5-dichlorophthalic acid and N{sub 2}H{sub 4}.H{sub 2}O. > In this article, a simple method to judge whether the polycarboxylic acid precursors have acylated into the acylhydrazidate ligands is introduced. > In this article, DFT calculations were carried out on the excited electronic states of the compounds, the fluorescence emission properties of the compounds have been better understood. > this article, by the structural characterization of the obtained monoacylhydrazidate-containing compounds, the character of the monoacylhydrazidate ligands has been further understood.« less

Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [W{sup VI}{sub 3}V{sup V}{sub 3}O{sub 19}H]{l_brace}[Cu(HDABCO)]{sub 2}(H{sub 2}O){r_brace} (1), [P{sub 2}Mo{sup VI}{sub 18}O{sub 62}][HDABCO]{sub 2}[H{sub 2}DABCO]{sub 2}.12 H{sub 2}O (2) and [Mo{sup VI}{sub 7.5}W{sup VI}{sub 0.5}O{sub 27}][Cu(HDABCO)]{sub 2}.2 H{sub 3}O.2 H{sub 2}O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the 'chains' arranged hexagonally, compound 3 contains [Mo{sub 7.5}W{sub 0.5}O{sub 27}]{sub {infinity}} chain decorated by [Cu(HDABCO)]{sup 2+} cations, which was then packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. -- Graphical abstract: Three new supramolecular compounds based on triethylenediamine and different polyoxometalates have been hydrothermally synthesized and characterized by IR, XPS, TG, elemental analysis and X-ray diffraction analysis.

A new compound [Mo8V7O42][Cu(2,2′-bpy)2]2[Cu(2,2′-bpy)]·2H3O (1) has been synthesized under hydrothermal conditions and characterized by IR, UV–vis spectrum, elemental analysis, XRD, ESR, XPS, X-ray diffraction analysis and magnetic property study. Single-crystal X-ray structure analysis indicates that the compound 1 is a novel Keggin polyoxoanion tri-supported mixed-valent transition metal coordination complex.

The hydrothermal reactions of Cul, KI and bidentate amines [1, 10-phenanthroline (phen) or ethylenediamine (en)] gave the three copper (I) halide compounds, Cu3I3 (phen)2 (1), CuI (phen)2 (2) and [Cu (en)2] [CuI2]2 (3), which were structurally characterized via single-crystal X-ray diffraction studies. Hydrogen bonds and τ-τ interactions are the most remarkable structural features of the title compounds. All can be described as higher-dimensional supramolecular compounds connected via these secondary bondings. Moreover, the title compounds were characterized by elemental analyses, IR spectra and TGA analyses. The third-order non-linear optical properties of the title compounds were also investigated and all exhibit nicer non-linear absorption and self-focusing performance.

The title compound Cu2Cl2phen (phen = 1,10-phenanthroline, C12H8N2) 1 was synthesized from CuCl2·2H2O, CuCl and phen by hydrothermal method and its structure was determined by single crystal X-ray analysis. With phen, CuG forms one-dimensional chains, which comprise two zigzag chains based on fused Cu-X units and connected via covalent bonds. The compound contains two crystallographically unique monovalent copper ions, Cu(1) and Cu(2). The Cu(1) atom in the tetrahedral site, is coordinated to two bridging Cl− and two N atoms in phen. The Cu(2) atom with a slightly distorted triangular planar geometry, is coordinated to three Cl−. The compound 1 was crystallized in monoclinic, space group P21/n with a = 0.37338(4), b = 1.9510(2), c = 1.68008(19) nm, β = 95.605 (3)°, R = 0.0458, and was characterized by elemental analysis, IR spectrum and TGA analysis.

Two compounds based on polyoxometalates, (4,4′-H2bpy)7(4,4′-Hbpy)[ ]2[ ] ·10H2O (1) and (4,4′-H2bpy)6(4,4′-bpy)[ ]2 · 18H2O (2), have been prepared under hydrothermal conditions and characterized by IR, XPS spectra, TG analyses, and single crystal X-ray diffraction. Both compounds consist of 4,4′-bipyridine units and polyoxometalates: [ ]5− for 1 and [ ]6− for 2. In addition, 1 contains both Keggin-type and disordered Keggin-type anions, while 2 contains a (H2O)10 water cluster.

Four inorganic–organic hybrid materials based on poly(oxomolybdophosphate) cluster building blocks have been obtained by hydrothermal methods. 1 shows a 2-D sheet structure, 2 and 3 possess 1-D chain structures and 4 is the discrete cluster. Crystal structural analysis reveals that the dimensionality and organization of those compounds can be tuned by the pH value of the reaction system. In addition, the fluorescence emissions are analysed of compounds 1, 2 and 4 containing Cd atoms with d10 electronic configuration red-shift along with the increase in the dimensions of those compounds.

Two new polyoxometalates [HN(C2H5)3]3[PMo12O40] (1) and [NH2(C2H4NH3)2]2[Mo5P2O23] (2) have been hydrothermally synthesized and characterized by IR, UV-Vis, XPS spectra, TG analyses, and single crystal X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c, a = 24.651(5) A, b = 10.822(2) A, c = 22.413(5) A, β = 120.37(3)°, and V = 5158.7(18) A3; for 2: triclinic, space group P-1, a = 9.821(2) A, b = 9.948(2) A, c = 14.687(3) A, α = 95.490(3)°, β = 98.870(3)°, γ = 95.710(3)°, and V = 1401.7(5) A3. The crystal structure analyses reveal complex hydrogen bonds in both 1 and 2 in 3-D supramolecular arrays constructed from different polyoxoanions and organic ligands.

A novel compound PMo 10 VI V 4 IV O 42 Co(Phen) 2 ( H 2 O ) 2 PMo 10 VI V 4 IV O 42 Co(Phen) 2 2 · 2 OH - · 4 , 4 -bpy 1 which represents the missing link between the discrete POMs and the POMs as building blocks in extended structure has already been hydrothermally synthesized and characterized by elemental analysis, IR, UV–Vis, XPS spectrum, TG analysis and single-crystal X-ray diffraction analysis. The study of the magnetic susceptibility of the compound 1 demonstrates the presence of ferromagnetic interactions.

Two supramolecular compounds [Fe(2,2′-bipy)3]2[ (Cl)] · 4.67H2O (1) and [Ni(enMe)3]2[ (Cl)] · 2H2O (2) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR, TGA, ESR, magnetic properties, and single crystal X-ray diffraction analyses. Crystal data for 1: tetragonal, I-42d, a = 13.6043(19), b = 13.6043(19), c = 50.544(10) A, V = 9354(3) A3; for 2: hexagonal, P6(3)/m, a = 12.6046(12), b = 12.6046(12), c = 22.563(5) A, V = 3104.4(7) A3. Compound 1 is constructed from cations [Fe(2,2′-bipy)3]3+, polyoxovanadates [ (Cl)]6−, and water molecules. Compound 2 is composed of cations [Ni(enMe)3]2+, clusters [ (Cl)]8−, and water molecules. There are hydrogen-bonding interactions between polyoxovanadates, organic moieties, and/or water molecules in 1 and 2, forming different 2-D layered networks.

A novel polyoxometalate { P 2 V W 18 VI Ni 4 ( H 2 O ) 2 O 68 [ Ni ( en ) 2 ( H 2 O ) ] 2 } [ Ni ( en ) 3 ] 2 [ Ni ( en ) 2 ( H 2 O ) 2 ] · 14 H 2 O (1) has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, ESR spectrum and single crystal X-ray diffraction analysis. It is a novel Weakley-type POM supported transition metal coordination complex, also it contains a novel (H2O)14 water cluster in the structure. The study of the magnetic susceptibility of 1 demonstrates the presence of ferromagnetic interactions.

Two new supramolecular compounds based on tungsten–vanadium polyoxoanions formulated as [Cu(2,2′-bipy) 3 ] 2 H 14 [PW 2.2 V 9.8 O 40 (VO) 2 [Cu(2,2′-bipy) 2 H 2 O] 2 ][PW 2.2 V 9.8 O 40 (VO) 2 ]·10H 2 O ( 1 ) and [Cu 4 (2,2′-bipy) 4 (H 2 O) 2 (PO 4 ) 2 ]H 6.5 [PW 8.4 V 3.6 O 40 ]·2H 2 O ( 2 ) (2,2′-bipy=2,2′-bipyridine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compounds 1 and 2 exhibit novel 2D supramolecular layer structures constructed from tungsten–vanadium polyoxoanions and different types of secondary building units (SBUs), respectively, the different SBUs are formed by [Cu(2,2′-bipy) 2 H 2 O] 2+ and [Cu(2,2′-bipy) 3 ] 2+ cations in compound 1 and [Cu 4 (2,2′-bipy) 4 (H 2 O) 2 (PO 4 ) 2 ] 2+ cations in 2 , respectively. Study of magnetic properties indicated the presence of antiferromagnetic behaviors for both compound 1 and 2 .

Two new polyoxometalates [ Ni ( phen ) 3 ] [ Ni ( en ) 3 ] [ Ni ( en ) 2 ( H 2 O ) 2 ] [ Ni ( en ) 2 ] 0.5 [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 6 H 2 O (1) and [ Ni ( phen ) 3 ] 2 [ Ni ( en ) 2 ] Na [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 8 H 2 O (2) (en=ethylenediamine, phen=1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, EPR, XPS, elemental analysis and thermogravimetry. Their structures exhibit interesting 3D supramolecular networks, and contain new bicapped (pseudo-) Keggin-type tungsten–vanadium cluster and the template transition-metal complexes (TMCs) being generated in situ under mild hydrothermal conditions. Interestingly, compound 1 contains four different kinds of nickel complex countercations.

Two new molybdenum–vanadium polyoxometalate tri-supported transition metal complexes [Cu(2,2 ′ -bipy)] [Cu(2,2 ′ -bipy) 2 ] 2 [PMo 8 V 6 O 42 ]· n H 2 O ( n = 1.5 ( 1 ) and n = 2 ( 2 ); 2,2 ′ -bipy = 2,2 ′ -bipyridine) have been hydrothermally synthesized and characterized by elemental analyses, IR, XPS and single-crystal X-ray diffraction analyses. Both compound 1 and compound 2 contain molybdenum–vanadium polyoxometalates, each of which support one [Cu(2,2 ′ -bipy)] 2+ cation and two [Cu(2,2 ′ -bipy) 2 ] 2+ cations, respectively. The difference between compound 1 and compound 2 is that the polyoxoanion of 1 is a bi-capped α-Keggin cluster and that of 2 is a bi-capped pseudo-Keggin one. Studies of magnetic properties indicated the presence of ferromagnetic behaviors for compounds 1 and 2 .

Two supramolecular architectures based on polyoxometalates: [4,4′-Hbpy]2[Ni(4,4′-bpy)2(H2O)4][AsWVI11WVO40]·4H2O (1) and [4,4′-H2bpy]2[PMoVI9MoV3O40]·2H3O (2) (4,4′-bpy = 4,4′-bipyridine) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, XPS spectra and single crystal X-ray diffraction analyses. The two compounds consist of 4,4′-bpy units with different polyoxometalates, α-Keggin [AsWVI11WVO40]4− and pseudo-Keggin [PMoVI9MoV3O40]6−, respectively. No direct interactions occur among polyoxoanions in these two compounds, but the clusters together with metal-organic units or organic 4,4′-bpy units and/or water molecules construct the high-dimensional supramolecular networks through hydrogen bonds. The crystal structure analyses reveal that the organic 4,4′-bpy units have a major influence on the packing arrangements of crystals.

A novel polyoxometalate {[Ni(enMe) 2 ] 2 [Ni(enMe) 2 (H 2 O)] 2 [As 2 W 18 Ni 4 (enMe) 2 O 68 ]}·2H 3 O·2H 2 O ( 1 ) (enMe = 1,2-propylenediamine) has been synthesized and characterized, which is the first high-dimensional structure constructed from sandwich-type transition metal substituted tungstates and transition metal coordination groups.

A novel polyoxometalate [Cu(en)2(H2O)]2[Cu(en)2]2 [AsW9V7O44] · 2H2O (1) has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, XPS spectrum and single crystal X-ray diffraction analysis. It is the first example of two-dimensional layer structure constructed from four vanadium-capped pseudo-Keggin tungstates. The study of the magnetic susceptibility of 1 demonstrates the presence of ferromagnetic interactions.

A novel polyoxometalate [Cu(phen)2]3{PW4VIW5VV3IVO40(VIVO)3[Cu(en)2]}⋅4H2O 1 (en=ethylenediamine, phen=1,10-phenanthroline) has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TG, EPR and single-crystal X-ray diffraction analysis. The crystal structure analysis shows that compound 1 contains a novel highly reduced tri-capped and mono-supported pseudo-Keggin-type heteropolyanion, {PW4VIW5VV3IVO40(VIVO)3[Cu(en)2]}6−, three [Cu(phen)2]2+ cations and four lattice water molecules. They are further linked to form three-dimensional supramolecular networks through extensive hydrogen bonding and π–π stacking interactions. Interestingly, the water dimer and terminal oxygen of the cluster polyanion constitute a beautiful supramolecular helix chain. The heteropolyanion is the first example of tri-capped and mono-supported pseudo-Keggin-type tungstovanadophosphate and the pH value is crucial for obtaining compound 1 in synthetic procedure.

Six new complexes constructed by 5-sulfosalicylic acid and bipyridyl-like ligands (2,2′-bipy and 1,10-phen), namely [Cu4(OH)2(ssal)2(phen)4 · 7H2O] (1), [Cu4(OH)2(ssal)2(bipy)4 · 2H2O] (2), [Cd(Hssal)(bipy)] (3), [Cd(HL)2(phen)2] (4), [Cr(ssal)(bipy)(H2O)2 · 2H2O] (5) and [Cr(ssal)(phen)2] (6) (H3ssal = 5-sulfosalicylic acid, H2L = p-hydroxybenzenesulfonic acid, bipy = 2,2′-bipy, phen = 1,10-phen) were prepared under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are both tetranuclear copper complexes with a stepped topology. In complex 3, a new coordination mode of the Hssal2− group is reported in this work. During the synthetic process of complex 4, in situ decarboxylation of 5-sulfosalicylic acid into p-hydroxybenzenesulfonic acid is involved. Two chromium 5-sulfosalicylates (5 and 6) are reported for the first time. These new complexes display different supramolecular structures by O–H⋯O, C–H⋯O hydrogen bonds as well as π⋯π, C–H⋯π and O⋯π interactions. The results of magnetic determination show that ferromagnetic interactions exist in complex 1, however, antiferromagnetic interactions exist in 2.

Three new molybdophosphates, [Co(dien){sub 2}].(H{sub 3}dien){sub 6}.{l_brace}[CoMo{sub 12}O{sub 24}(OH){sub 6}(HPO{sub 4}){sub 2}(PO{sub 4}){sub 6}][Co(Hdien)]{sub 2}[CoMo{sub 12}O{sub 24} (OH){sub 6}(PO{sub 4}){sub 8}]{r_brace}.(dien).4H{sub 3}O.5H{sub 2}O (1) (H{sub 3}dien){sub 4}[MMo{sub 12}O{sub 24}(OH){sub 6}(HPO{sub 4}){sub 4}(PO{sub 4}){sub 4}].10H{sub 2}O [M=Co for (2), Ni for (3); dien=diethylenetriamine], have been synthesized by employing hydrothermal method and characterized by single crystal X-ray diffraction. Compound 1 is built up of Co[P{sub 4}Mo{sub 6}]{sub 2} units as the structural motif covalently linked by [Co(Hdien)] complex subunits to yield an unusual 1-D chain. Compounds 2 and 3 are isomorphic and both display covalent discrete M[P{sub 4}Mo{sub 6}]{sub 2} cluster structures which are linked by the hydrogen bonds to form 3-D supramolecular networks. Both 1 and 2 display antiferromagnetic interaction and these three compounds all exhibit intensive photoluminescence. - Graphical abstract: Three new reduced molybdophoshpates based on P{sub 4}MO{sub 6} building blocks have been hydrothermally synthesized. 1 is the first covalent 1-D chain consisting of two kinds of forms of M[P{sub 4}MO{sub 6}]{sub 2} units, standing forms A and lying forms B, while 2 and 3 possess 3-D supramolecular network structures. These three compounds all display photoluminescence.

A new 3D supramolecular framework, Ni ( en ) 2 3 V IV 11 V V 7 O 42 Cl · 8 H 2 O (1) (en = ethylenediamine), has been hydrothermally synthesized and characterized by elemental analysis, IR, XPS, TG and single crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group C2/c, a = 12.735(3), b = 26.976(5), c = 21.171(4) A, β = 92.64(3)°, V = 7265(2) A3, and Z = 4. Complex 1 exhibits an interesting three-dimensional supramolecular framework assembled by sinusoidal-like arrangement of two-dimensional coordination polymer layers and crystal water molecules. The magnetic behavior of 1 has also been studied.

Five cadmium halides with N-donor ligands were synthesized under the hydrothermal conditions and characterized by X-ray single-crystal diffraction. The isostructural [CdX2(2,2′-bpy)] (X = I 1, Br 2, bpy = bipyridine) (1) possess 3-D supramolecular network structures based on 1-D zigzag-type CdX2 chains extended by bpy molecules via non-covalent C–H⋯X hydrogen-bonded interactions. The 3-D porous [CdBr2(pip)] (pip = piperazine) (3) is formed through a linkage of 1-D zigzag-type CdBr2 chains by pip bridges. The heteronuclear dimetal–iodo cluster [Cu(phen)2CdI4] (phen = phenanthroline) (4) consists of a trigonal bipyramidal Cu(II) center and a tetrahedral Cd(II) center linked by a μ2–I bridge. The ionic [Co(dien)2][CdI4] (dien = diethylenetriamine) (5) comprises an octahedral CoN 6 2 + cation and a tetrahedral CdI 4 2 - anion.

The title layered double salt Mn3(OH)2(SO4)2(H2O)2 · K2SO4 (1) was obtained from a simple hydrothermal reaction of CdSO4 · 8/3H2O, MnCl2 · 4H2O, α-aminopyridine (apy) and KI. X-ray analysis reveals that the two-dimensional (2-D) sheet of 1 is built up of the dimers of edge-sharing Mn(1) octahedral, extended by the apices of Mn(2) octahedral together with μ3 and μ4 SO4 groups. With free K+ ion as guest species, the 2-D sheets are further self-assembled into a 3-D supramolecular network with 1-D channels through the Ow-H ⋯ O hydrogen-bonded interactions. The magnetic property of 1 was investigated, and a classical behavior is observed with an antiferromagnetic order below 12.5 K.

Two supramolecular compounds based on Keggin polyoxotungstates, (4,4′-H2bpy){[Cu(4,4′-bpy)]2[SiW12O40]} (1) and (4,4′-H2bpy)2[SiW12O40]·2H2O (2) have been synthesized and characterized by elemental analyses, IR, UV, XPS spectra, TG analyses, and single crystal X-ray diffraction analyses. Compound 1 exhibits an infinite 1-D ladder like structure, which is further interconnected into a 3-D supramolecular framework via hydrogen bonding interactions. Compound 2 contains 4,4′-bipyridine (4,4′-bpy), pseudo-Keggin polyoxoanions [SiW12O40]4−, and water molecules. Polyoxoanions together with water molecules in 2 construct a 3-D inorganic supramolecular network through O···O and O···Ow(1) interactions. The electrochemical behaviors and photocatalytic properties of 1 and 2 have been investigated.

Four oxalate-bridged transition-metal supramolecular compounds [Co2(im)4(ox)2] 1, [Co(im)2(ox)] 2, [Mn(2,2′-bpy)(ox)] 3 and [Fe(H2O)2(ox)] 4 (im, imidazole; ox, oxalate; bpy, bipyridine) were obtained from the simple hydrothermal reactions of Mn+ ox L (M, transition metal; L, aromatic N-donor ligand) system. They all exhibit the 1-D chain structures, consisting of the ML 2 2 + (or ML2+) units linked by oxalate bridges. Interestingly, the 1-D oxalate chains in the title compounds are further self-assembled into the 3-D supramolecular networks through the interchain various secondary bonding interactions. Because the ML 2 2 + units adopt the different configuration, the oxalate chains show either zigzag type as in compounds 1–3 or linear type as in compound 4. Compounds 1 and 2 are isomeric, and only in packing modes of interchain im molecules there exists the difference.

Three compounds based on polyoxometalate building blocks, [Cu(en) 2 ]{[Cu(en) 2 ] 2 [Mo VI 5 Mo V 3 V IV 8 O 40 (PO 4 )]} · 4H 2 O ( 1 ), [Co(en) 2 ]{[Co(en) 2 ] 2 [HMo VI 4 Mo V 4 V IV 8 O 40 (PO 4 )]} · 5H 2 O ( 2 ) and [Ni(en) 2 ]{[Ni(en) 2 ] 2 [Mo VI 5 Mo V 3 V IV 8 O 40 (VO 4 )]} · 2H 2 O ( 3 ) (en = ethylenediamine), have been synthesized and characterized by elemental analysis, IR, XPS, XRD, TGA and single-crystal X-ray diffraction analysis. The result of structure determination shows that isomorphic compounds 1 , 2 and 3 feature a one-dimensional chain built from the reduced tetra-capped pseudo-Keggin polyoxoanion, which is further interconnected by [M(en) 2 ] 2+ (M = Cu, Co and Ni) groups via the terminal oxygen atoms of polyoxoanions. The crystal data for these compounds are the following: 1 , monoclinic, space group C2 / c , a = 26.702(3) A, b = 13.4539(14) A, c = 19.5987(19) A, β = 108.650(2)°, V = 6671.0(12) A 3 , Z = 4; 2 , monoclinic, space group C2 / c , a = 26.244(3) A, b = 13.5070(17) A, c = 19.581(3) A, β = 106.881(2)°, V = 6641.8(15) A 3 , Z = 4; 3 , monoclinic, space group C2 / c , a = 26.2789(15) A, b = 13.5408(6) A, c = 19.6312(9) A, β = 106.2590(10)°, V = 6706.1(6) A 3 , Z = 4. Variable-temperature magnetic susceptibility measurements of compounds 1 and 3 reveal the feature of antiferromagnetic exchange in these compounds.

A novel polyoxometalate ( C 2 N 2 H 9 ) 2 [ PMo 5 V Mo 7 VI Sb 2 III O 40 ] · 2 H 2 O (1) has been synthesized in the system of Sb2O3-(NH4)6Mo7O24 · 4H2O-H3PO4-en-H2O under hydrothermal conditions and characterized by IR, TGA, elemental analyses, single crystal X-ray diffraction and XPS. Interestingly, compound 1 displays three-dimensional network consisting of one-dimensional sinusoidal chain [(Hen)2(H2O)2]2+ and two-dimensional layer formed by [ PMo 5 V Mo 7 VI Sb 2 III O 40 ] 2 - . The structure unit [ PMo 5 V Mo 7 VI Sb 2 III O 40 ] 2 - is the first example of bicapped by antimony α-Keggin structure.

Two new heteropoly tungstovanadate derivatives, [Fe(phen)3]2[W10.5V4.5O42]·3H2O (1) and [Fe(phen)3]2[W10V5O42].6H2O (2) (phen=1,10′-phenanthroline), have been synthesized under hydrothermal conditions by using different starting materials, and characterized by elemental analysis, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analysis. Crystal data for compound 1: C72H54Fe2N12O45V4.5W10.5, monoclinic, space group C2/c, a = 30.244 ( 9 ) A , b = 13.586 ( 3 ) A , c = 24.707 A , β = 99.882 (8)°, V = 10002 (5) A3, Z = 4 ; for compound 2, C72H60Fe2N12O48V5W10, monoclinic, space group C2/c, a = 30.246 (6) A, b = 13.909 ( 3 ) A , c = 25.329 (5) A, β = 100.34 (3)°, V = 10483 (4) A3, Z = 4 . The crystal structure analysis reveals that both polyoxoanions are decorated with the [Fe(phen)3]2+ cations, and that they have analogous structure to each other with slightly different packing modes of the polyoxoanions, [Fe(phen)3]2+ cations and water molecules. They are further linked to form two-dimensional (2D) supramolecular networks through extensive hydrogen bonding.

The new polyoxometalate double-supporting transition metal complexes, {[Co(phen)2]2C2O4} {H2P O44[Co(phen)2H2O]2}·7H2O (1) (phen = 1,10-phenanthroline) have been hydrothermally synthesized and characterized by single crystal X-ray analysis, IR, XPS, ESR and elemental analysis. Compound 1 is composed of a highly reduced tetra-capped pseudo-Keggin polyoxoanion supporting two transition metal complexes, a binuclear cobalt complex cation and lattice water. The magnetism and third-order non-linear optical properties of 1 have also been studied.

Two interesting coordination polymers, [Ag8(IN)6(NO3)2] 1 and [Ag(IN)(HIN)]1/2 [Ag(IN)] 2 (HIN=isonicotinic acid) have been synthesized hydrothermally at different pH values. 1 crystallizes in the triclinic space group P-1, with a = 10.987 ( 2 ) A , b = 11.625 ( 2 ) A , c = 17.323 ( 4 ) A , α = 75.87 ( 3 ) ° , β = 80.87 ( 3 ) ° , γ = 76.50 ( 3 ) ° , V = 2074.0 ( 7 ) A 3 and Z = 2 . Compound 1 is the first example of a bilayer framework, in which both single layers are connected by the bond interactions (Ag–O) between Ag from two two-dimensional (2D) single layers generated by the A building block and O atoms from one-dimensional (1D) chain constructed by the B building block, in which coordination modes of IN were reported for the first time. 2 crystallizes in the monoclinic space group P2(1)/c, with a = 8.1668 ( 16 ) A , b = 19.611 ( 4 ) A , c = 7.4083 ( 15 ) A , β = 92.90 ( 3 ) ° , V = 1185.0 ( 4 ) and Z = 4 . Compound 2 exhibits a 2D plywood-like structure assembled by hydrogen bonds and weak Ag–O interactions.

A new metal-oxo cluster supported transition metal complex, [Cu(en)2(H2O)]2[Cu(en)2]0.5[MoVI8VIV6VVO42{Cu(en)2}], has been synthesized under hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in the triclinic system, space group (No. 2), a = 12.245(5), b = 12.669(5), c = 20.949(8) A, α = 77.120(13), β = 78.107(17), γ = 65.560(14)°, V = 2860(2) A3, Z = 2. The metal-oxo cluster contains a novel bicapped a-Keggin structure unit and a [Cu(en)2]2+ unit covalently bonded to the [Mo8V7O42]7− cluster.

Two new interesting polyoxometalate derivatives { [ Ni ( 2 , 2 ′ ‐ bipy ) 2 H 2 O ] 2 [ Mo 3 V Mo 5 VI V 8 IV O 40 ( PO 4 ) ] } { [ Ni ( 2 , 2 ′ ‐ bipy ) 2 H 2 O ] 2 [ Mo 3 V Mo 5 VI V 8 IV O 40 ( PO 4 ) ] } · 5 H 2 O 1 and { [ Co ( 2 , 2 ′ ‐ bipy ) 2 H 2 O ] 4 [ Mo 4 V Mo 4 VI V 8 IV O 40 ( PO 4 ) ] } { [ Co ( 2 , 2 ′ ‐ bipy ) 2 H 2 O ] 2 [ Mo 3 V Mo 5 VI V 8 IV O 40 ( PO 4 ) ] } ( H 3 O ) · 4 H 2 O 2 constructed of modified metal–oxo cluster ions carrying positive and negative changes, respectively, was hydrothermally prepared and structurally characterized by IR, ESR, XPS, elemental analysis and X-ray crystallography. The result of structure determination shows that compound 1 and 2 are isostructural and both contain polyoxocation and polyoxoanion, and both cation and anion are built on mixed Mo–V tetra-capped pseudo-Keggin units with P centre, [Mo8V8O40(PO4)]n−, bonded to four or two [Ni(2,2′-bipy)2H2O]2+ complexes, respectively, via terminal oxygen of the capping V atoms. Magnetism measurement indicates that there exists antiferromagnetic interaction in complex 1 and 2.

Two new arsenic–vanadium clusters, [Co(2,2′- bpy)3]2[As8V14O42(H2O)] · 3H2O (1), [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)] · 3H2O (2) (2,2′-bpy=2,2′-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) A, b=16.753(3) A, c=24.632(5) A, α=94.15(3)°, β=93.16(3)°, γ=113.05(3)°, Z=2; 2, monoclinic, P21/c, a= 30.2150(4) A, b=14.0690(3) A, c=26.0536(3) A, β=106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As8V14O42(H2O)]4− and transition metal coordination complexes [M(2,2′-bpy)3]2+ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2′-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2′-bpy/arsenate polyoxometallates.

The hydrothermal reaction of CuBr2, CuBr and 1,10-phen gives birth to a 2-D coordination polymer [ Cu 4 II ( OH ) 4 (1,10-phen)4][ Cu 8 I Br 12 ] (1), consisting of the unique [ Cu 8 I Br 12 ] 4 - chains linked by the stepped-cubane copper(II)-hydroxo clusters [ Cu 4 II ( OH ) 4 ( phen ) 4 ] 4 + as the bridges. Compound 1 possesses high thermal stable. The non-linear optical property of 1 was studied, and the compound exhibits the reverse saturable absorption (α2 = 0.80 × 10−11 m W−1) and self-defocusing performance (n2 = −1.55 × 10−18 m2 W−1).

A novel cobalt phosphomolybdate: (NH 3 CH 2 CH 2 NH 3 )(NH 3 CH 2 CH 2 NH 2 ) 3 Na 3 [Co 4 Mo 12 O 24 (OH) 6 (H 2 O) 2 (HPO 4 ) 2 (PO 4 ) 6 ]·8H 2 O 1 , has been hydrothermally synthesized (200°C, 5 days, autogenously pressure) and characterized by IR, ESR, XPS, elemental analyses and X-ray crystallography. The crystal data: monoclinic space group C 2/ c , a =12.3281(3) A, b =21.5729(4) A, c =26.0242(5) A, β =99.5401°(3), V =6825(2) A 3 , Z =4, R 1 =0.0346, w R 2 =0.0650. The structure of compound 1 is based on Co[Mo 6 P 4 ] 2 units connected together via additional Co 2+ ions to give a new three-dimensional framework. The interconnected void and channels in the cobalt molybdophosphate frameworks are filled with counter cations and water molecules. The magnetic property of 1 exhibits antiferromagnetic coupling interactions.

Two novel coordination polymers of cobalt(II), [Co(µ3-H2bbh)(phen)]n (1) and [Co(µ4-H2bbh) (H2O)2]n (2) (phen = 1,10-phenanthroline; H4bbh = benzene-1,2,4,5-tetracarbo-1,2:4,5-dihydrazide), in which H2bbh ligands are in situ generated by an acylation reaction of H4bta (H4bta = benzene-1,2,4,5-tetracarboxylic acid) with hydrazine hydrate under hydrothermal conditions have been synthesized and structurally characterized. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

A novel polyoxometalate compound, [As8V14O42(SO4)][Ni(en)2]3·4.5H2O (1), has been synthesized by a hydrothermal method and characterized by X-ray crystallography, showing that the compound 1 is the first example of a sinusoidal layer structure constructed from polyoxometalates and coordination complex fragments. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

A novel cerium–adipate coordination polymer [Ce2(ad)3(H2O)2]n(1) has been hydrothermally synthesized and structurally characterized, which possesses three-dimensional network structure constructed from infinite chains of edge-sharing CeO8(H2O) polyhedron and long carbon chains. Each cerium cation binds to nine oxygen atoms belonging to six adipates and one water molecule, the adjacent cerium atoms are linked together through chelating-bridging and bidentate bridging carboxylates to form infinite polyhedron chains along [1 0 0] direction. The starlike distribution of six μ4-adipates around the central cerium generates a complicated network, which is thermally stable without any collapse even though no any guest molecules reside in the large channels.