Syntheses, structures and properties of two new neodymium complexes with N-P-acetamidobenzenesulfonyl-glycine acid

Two new neodymium complexes, [Nd₂(abglyH)₆(2,2′-bipy)₂(H₂O)₂] · 4H₂O 1 and {[Nd(abglyH)₃(H₂O)₂] · (4,4′-bipy) · 7H₂O}_n 2 (abglyH₂ = N-P-acetamidobenzenesulfonyl-glycine acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and their structures have been measured by X-ray crystallography. In 1, nine-coordinated Nd(III) ions are bridged by two syn–syn bidentate and two tridentate bridging carboxylate groups from four different abglyH⁻ anions to form dinuclear motifs, which are further connected into a 3-D supramolecular framework via hydrogen bonds between the binuclear motifs and the uncoordinated water molecules. In 2, eight-coordinated Nd(III) ions are linked by six carboxylate groups adopting a syn–syn bidentate bridging fashion to form a 1-D inorganic–organic alternating linear chain. These polymeric chains generate microchannels extending along the a direction, and these cavities are occupied by discrete tetradecameric water clusters, which interact with their surroundings and finally furnish the 3-D supramolecular network via hydrogen bonds. At the same time, π–π stacking interactions between benzene rings from abglyH⁻ anions also play an important role in stabilizing the network.     

Novel Hybrids Constructed from Keggin-Polyoxometalate and Mixed Copper Complex

Abstract  Two new Keggin-polyoxometalate hybrids, {[Cu₂(4,4′-bpy)₂][PW₁₀^VIW₂^VO₄₀]}[Cu₂(obpy)₂]₄ · 2 H₂O (1) and {[Cu₄(2,2′-bpy)₄(4,4′-bpy)₃][SiW₁₂O₄₀]} · 2H₂O (2) (4,4′-/2,2′-bpy = 4,4′-/2,2′-bipyridyl, Hobpy = 6-hydroxy-2,2′-bipyridyl), were hydrothermally synthesized and structurally characterized. Gillard type hydration of 2,2′-bipy is observed during the synthesis of 1, resulting in a new obpy ligand in situ. X-ray structural analyses show that 1 consists of 1D hybrid chain {[Cu₂(4,4′-bpy)₂][PW₁₀^VIW₂^VO₄₀]}_∞ and [Cu₂(obpy)₂] dimer, whereas 2 possesses 1D hybrid structure based on Keggin-type [SiW₁₂O₄₀]⁴⁻ anions and tetra-nuclear copper complexes [Cu₄(2,2′-bpy)₄(4,4′-bpy)₃]⁴⁺. Both compounds present interesting supramolecular architectures based on π–π stacking and hydrogen bonds. Graphical Abstract  Compounds {[Cu₂(4,4′-bpy)₂][PW₁₂O₄₀]}[Cu₂(obpy)₂]₄ · 2H₂O (1) and [Cu₄(2,2′-bpy)₄(4,4′-bpy)₃][SiW₁₂O₄₀] · 2H₂O (2) were hydrothermally synthesized. 1 features that the [Cu₂(obpy)₂] dimers based on in situ generated obpy ligands are stumped between the layers where 1D hybrid chain {[Cu₂(4,4′-bpy)₂][PW₁₂O₄₀]}_∞ locates, while 2 exhibits 1D chain-like structure based on anions [SiW₁₂O₄₀]⁴⁻ and tetra-copper complexes [Cu₄(2,2′-bpy)₄(4,4′-bpy)₃]⁴⁺.      

Synthesis,structures and electrochemical properties of four organic–inorganic hybrid polyoxometalates constructed from polyoxotungstate clusters and transition metal complexes

Four novel organic–inorganic hybrid compounds [Cu₅ ^I(4,4′-bpy)₃(2,2′-bpy)₄][BW₁₂O₄₀] · H₂O (1), [Ni_0.5(2,2′-bpy)_1.25][Ni(2,2′-bpy)₃][Ni(2,2′-bpy)₂(H₂O)(SiW₁₁^VIW^VO₄₀)] · 0.5H₂O (2), [H₂bpy]₂[Zn(2,2′-bpy)₃]₂[Si₂W₁₈O₆₂] · 1.5H₂O (3) and [Cu^II(2,2′-bpy)₂]₂[SiW₁₂O₄₀] · 2H₂O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW₁₂O₄₀]⁵⁻ polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW₁₁^VIW^VO₄₀]⁵⁻ polyoxoanions supported by [Ni(2,2′–bpy)₂]²⁺. Compound (3) is composed of a novel [Si₂W₁₈O₆₂]⁸⁻ cluster and [Zn(2,2′–bpy)₃]²⁺ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)₂]²⁺ coordination polymer fragments, resulting in 3D networks via supramolecular interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis,characterization and magnetic properties of supramolecular metal–organic complexes constructed from flexible–rigid mixed ligands

Two new supramolecular metal–organic complexes have been synthesized under hydrothermal conditions. Complex 1 exhibits a three-dimensional supramolecular network, constructed from [Co₂(H₃BPTC)₂(phen)₂] (H₄BPTC = 3,3′4,4′-benzophenone tetracarboxylate acid, phen = 1,10-phenanthroline) discrete units. Complex 2 similarly exhibits discrete [Cu₂(DPA)₂(bipy)₂(H₂O)₂] (DPA = 1,1′-biphenyl-2,2′-dicarboxylate acid, bipy = 2,2′-bipyridine) units, which are linked to form a three-dimensional supramolecular network through π–π interactions. It is interesting that during the synthesis of complex 1, the H₄BPTC ligands undergo partial decomposition to give 1,2,4-benzenetricarboxylate (H₃BTC) ligands, which react with Co to form [Co₃(BTC)₂]_n (3). Complex 3 shows a three-dimensional covalent network. The magnetic properties of complexes 1 and 2 have been studied.     

Studies on the magnetic properties of two cobalt(II) complexes bearing 1,4-phenylenediacetate ligands

One reported compound [Co(PDA)(4,4′-bipy)]_n·nH₂O and one new compound [Co(PDA)(Im)₂(H₂O)₂]_n·nH₂O were prepared by the reactions of Co(NO₃)₂·6H₂O or Co(OH)₂ with 1,4-phenylenediacetic acid (H₂PDA) in the presence of the ancillary ligands 4,4′-bipyridine (4,4′-bipy) or imidazole (Im), and their magnetic properties were investigated. The presence of 4,4′-bipy in [Co(PDA)(4,4′-bipy)]_n·nH₂O results in a μ ₃-bridging mode of the PDA²⁻ ligand with one μ ₂-carboxylato group and one chelating carboxylato group and the construction of a 2D framework as reported in the literature. The introduction of Im ligand in [Co(PDA)(Im)₂(H₂O)₂]_n·nH₂O helps to construct a one dimensional chain with the two carboxylato groups of PDA²⁻ ligand in monodentate coordination modes. The magnetic studies reveal the presence of dominant antiferromagnetic interaction in [Co(PDA)(4,4′-bipy)]_n·nH₂O with a field-induced magnetic transition due to spin-flop. Magnetically, [Co(PDA)(Im)₂(H₂O)₂]_n·nH₂O presents a mononuclear structure. This work reveals that the introduction of ancillary ligands in the Co(II)-PDA system adjusts the linking modes of PDA²⁻ and therefore the resulting frameworks and their magnetic properties.     

Self-assembly of four new extended architectures based on reduced polyoxometalate clusters and cadmium complexes

Four new [P₄Mo₆] cluster-based extended structures containing cadmium complexes, [Cd₃(4,4′-Hbpy)₂(4,4′-bpy)₂(H₂O)₈][Cd(H₂PO₄)₂(HPO₄)₄(PO₄)₂(MoO₂)₁₂(OH)₆]·7H₂O 1, (4,4′-Hbpy)₂[Cd(4,4′-bpy)₃(H₂O)₃][Cd(4,4′-bpy)(H₂O)]₂[Cd(H₂PO₄)₂(HPO₄)₄ (PO₄)₂(MoO₂)₁₂(OH)₆]·H₂O 2, [Cd₄(phen)₂(H₂O)₄][Cd(phen)(H₂O)]₂[Cd(HPO₄)₄ (HPO₄)₄(MoO₂)₁₂(OH)₆]·5H₂O 3 and [Cd₄(2,2′-bpy)₂(H₂O)₄][Cd(2,2′-bpy)(H₂O)]₂ [Cd(HPO₄)₄(HPO₄)₄(MoO₂)₁₂(OH)₆]·3H₂O 4 (4,4′-bpy=4,4′-bpyridine, phen=1,10-phenanthroline, 2,2′-bpy=2,2′-bpyridine), have been synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The structure of compound 1 is constructed from the Cd[P₄Mo₆]₂ dimers linked by [Cd₃(4,4′-Hbpy)₂(4,4′-bpy)₂(H₂O)₈] subunits to generate a plane layer. Compound 2 consists of the positive 2D sheets that constructed from Cd[P₄Mo₆]₂ dimers linked by [Cd(4,4′-bpy)(H₂O)] complexes, then the 2D sheets are further linked up together to form a 3D supramolecular framework via extensive hydrogen-bonding interactions among the [P₄Mo₆] clusters, free 4,4′-bpy molecules, dissociated [Cd(4,4′-bpy)₃(H₂O)₃]²⁺ complexes and water molecules. Compounds 3 and 4 show new 2D layered structure, with Cd[P₄Mo₆]₂ building blocks connected by tetra-nuclear [Cd₄{(phen)₂/(2,2′-bpy)₂}(H₂O)₄] clusters and [Cd(phen/2,2′-bpy)(H₂O)] complexes. The fluorescent activities of compounds 3 and 4 are reported.     

Two New 2D and 1D Ni(II) Coordination Polymers Bridged by Vanadium-Substituted Keggin Polyoxotungstophosphates: Hydrothermal Synthesis and Crystal Structure

Two coordination polymers based on vanadium-substituted Keggin polyoxotungstophosphates as bridging ligands, {[Ni(4,4′-bipy)_1.5(OH)(H₂O)]₂[H₃PW₁₀V₂O₄₀]}·4H₂O (4,4′-bpy = 4,4′-bipyridine) 1 and {[Ni(dpa)₂][Ni(dpa)(H₂O)₃]₂[PW₉V₃O₄₀]}·4H₂O (dpa = 2,2′-dipyridylamine) 2, have been obtained by hydrothermal reactions and characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray Diffraction analysis. Compound 1 is a 2D layered structure built from 1D infinite zigzag {Ni₂(4,4′-bipy)₃(OH)₂(H₂O)₂}_n²⁺ chains bridged via [H₃PW₁₀V₂O₄₀]²⁻ anions. Compound 2 exhibits a one-dimensional chain-like structure constructed from [Ni(dpa)₂]²⁺ fragments bridged via bis-supported Keggin polyoxoanions [Ni(dpa)(H₂O)₃]₂[PW₉V₃O₄₀]²⁻. The two examples demonstrate that vanadium-substituted Keggin polyoxometalates have greater coordination capability.     

Synthesis, characterization and properties of β-octamolybdate-supported transition metal complexes with mixed ligands: [Cu(2,2′-bipy)(C6H5NO2)(H2O)]2[Mo8O26]·5H2O

A novel organic–inorganic hybrid compound [Cu(2,2′-bipy)(C₆H₅NO₂)(H₂O)]₂[Mo₈O₂₆]·5H₂O (1), (2,2′-bipy = 2,2′-bipyridine; C₆H₅NO₂ = pyridine-4-carboxylic acid) has been prepared and characterized by elemental analyses, IR spectrum, thermal stability analysis, and single-crystal X-ray diffraction. Compound 1 is a discrete cluster, constructed from β-[Mo₈O₂₆]⁴⁻ subunits covalently bonded to two [Cu(2,2′- bipy)(C₆H₅NO₂)(H₂O)]₂⁴⁺ coordination cations via terminal oxo groups that connect one molybdenum site. A 3D supramolecular network is further formed by extensive hydrogen bonding interactions and π–π interactions of the 2,2′-bipy and pyridine-4-carboxylic acid ligands. EPR and magnetic susceptibility studies have been used to elucidate the electronic properties of the Cu²⁺ centres, and the results are in good agreement with the structural features of the compound.     

The construction of two lanthanide coordination polymers based on 5-hydroxyisophthalate and bipyridine

Two lanthanide coordination polymers, [Tm₂·(5-IPA)₄·(2,2′-Hbipy)₂]·3H₂O (1, 5-H₂IPA?=?5-hydroxyisophthalic acid, 2,2′-bipy?=?2,2′-bipyridine) and [Er·(5-HIPA)₃·(4,4′-bipy)₃·(H₂O)₂]·3H₂O (2, 4,4′-bipy?=?4,4′-bipyridine), have formed by hydrothermal synthesis. Complex 1 exhibits a 2-D coordination network containing parallelepiped-shaped voids occupied by guest 2′2-bipy molecules. Complex 2 possesses a 1-D linear chain structure. The 1-D chains are linked by 4,4′-bipy molecules to form a 3-D supramolecular framework. IR spectroscopy, elemental analysis, and thermogravimetric analysis were also investigated.     

Synthesis and crystal structures of 3D supramolecular compounds: [ M (4,4′-bipy)2(H2O)4] · (4,4′-bipy)2 · (3,5-daba)2 · 8H2O ( M =Zn,Mn)

Two new supramolecular compounds [M(4,4′-bipy)₂ (H₂O)₄] ·?(4,4′-bipy)₂ ·?(3,5-daba)₂ ·?8H₂O (M=Zn(1) or Mn(2), 4,4′-bipy =?4,4′-bipyridine, 3,5-daba =?3,5-diaminobenzoic acid anion) were synthesized and characterized by elemental analysis and X-ray crystal diffraction. In [M(4,4′-bipy)₂(H₂O)₄]²⁺, the M(II) is coordinated by two nitrogen atoms from two 4,4′-bipy molecules and four oxygen atoms from four waters to form an octahedral configuration. There exist uncoordinated 4,4′-bipy molecules, 3,5-diaminobenzolate counterions and water guests in the compounds. The 3D structures of the title supramolecular compounds are constructed by rich hydrogen bonds among [M(4,4′-bipy)₂(H₂O)₄]²⁺, uncoordinated 4,4′-bipy molecules, water molecules and 3,5-daba, containing a diverting hexa-member water ring.     

Syntheses,crystal structures and antibacterial activities of M(II) benzene-1,2,3-triyltris(oxy)triacetic acid complexes

Four metal(II) complexes with benzene-1,2,3-triyltris(oxy)triacetic acid (H₃L), {[Co_1.5(L)(H₂O)₆]·6H₂O}_n (1), {[Co_1.5(L)(4,4′-bipy)_1.5(H₂O)₄]·4H₂O}_n (2), {[Co(HL)(2,2′-bipy)(H₂O)₂]·1.5H₂O}_n (3), and {[Cu(HL)(phen)(H₂O)₂]·H₂O}_n (4) (4,4′-bipy = 4,4′-bipyridine; 2,2′-bipy = 2,2′-bipyridine; phen = phenanthroline), were prepared and structurally characterized. Complex 2 displays a 1-D structure, while 1, 3, and 4 reveal 0-D structures, which further extend to 3-D supramolecular networks by hydrogen bonding interactions, of which 1 and 4 contain double-helical chains, 2 includes meso-helices, and 3 comprises single-helices. Furthermore, the thermal stabilities and antibacterial activities of the complexes were studied.     

Two new hydrogen bond-supported supramolecular compounds assembly from tungsten-vanadium polyoxoanions and copper complex fragments

Two new supramolecular compounds based on tungsten-vanadium polyoxoanions formulated as [Cu(2,2′-bipy)₃]₂H₁₄[PW_2.2V_9.8O₄₀(VO)₂[Cu(2,2′-bipy)₂H₂O]₂][PW_2.2V_9.8O₄₀(VO)₂]·10H₂O (1) and [Cu₄(2,2′-bipy)₄(H₂O)₂(PO₄)₂]H_6.5[PW_8.4V_3.6O₄₀]·2H₂O (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)₂H₂O]²⁺ and [Cu(2,2′-bipy)₃]²⁺ cations in compound 1 and [Cu₄(2,2′-bipy)₄(H₂O)₂(PO₄)₂]²⁺ cations in 2, respectively. Study of magnetic properties indicated the presence of antiferromagnetic behaviors for both compound 1 and 2.     

Synthesis and characterization of a novel Anderson-type tungstotellurate decorated by transition metal complexes: [Na(H2O)3]2[{Cu(2,2′-bipy)2}2(TeW6O24)]?·?4H2O

A novel organic–inorganic hybrid tungstotellurate [Na(H₂O)₃]₂[{Cu(2,2′-bipy)₂}₂(TeW₆O₂₄)] · 4H₂O, has been synthesized and characterized by elemental analyses, IR spectra, TG analyses, and single-crystal X-ray diffraction. The saturated Anderson-type polyoxoanions are covalently bonded with two [Cu(2,2′-bipy)₂]²⁺, and linked by Na⁺ into an infinite one-dimensional chain. Furthermore, the three-dimensional supramolecular architectures are formed by π–π stacking interactions of the 2,2′-bipyridine groups between adjacent layers and the hydrogen-bonding interactions respectively.     

Two 3D supramolecules with helices constructed by hydrogen bonds based on p-thioacetatebenzoic acid ligand

Abstract  

p-Thioacetatebenzoic acid (H₂L) and a combination of N-donor ligands such as 4,4′-bipyridine (4,4′-bipy) and 1,3-bi(4-pyridyl)propane (bpp) with metal ions Mn(II) and Ni(II) give rise to two coordination polymers, namely, [Mn(HL)₂(bpp)₂(H₂O)₂] _n (1), [NiL (4,4′-bipy)(H₂O)₃] _n ·nH₂O (2). 1 features an unusual “8” shaped double layer by hydrogen bonds and two different types of helical chains are arrayed alternatively in the 2D double layer framework, which further extends into a 3D supramolecular structure through C–H···O hydrogen bonds. 2 consists of 1D chains which further connect with each other via hydrogen bonds to form the final 3D framework including two different types of helical structure. Photoluminescence study reveals that 1 displays intense structure-related fluorescent emission bands (λ _ex = 369 nm) at 414 nm in the solid state at room temperature. Electrochemical property of 2 reveals that the process of the redox is irreversible.     

Three isostructural 3D supramolecules with <Emphasis Type="Italic">p</Emphasis>-thioacetatebenzoic acid ligand: syntheses,structure characterizations,and properties

Abstract  

p-Thioacetatebenzoic acid (H₂L) and a combination of N-donor ligand of 4,4′-bipyridine (4,4′-bipy) with metal(II) ions give rise to three 3D supramolecules of general formula [M(HL)₂(4,4′-bipy)₂(H₂O)₂] · H₂O, M = Co^II (1), Zn^II (2), Ni^II (3), which were characterized by crystallographic methods. The crystals are isostructural and belong to the triclinic P[`1] P\bar{1} space group. The structure can be considered to construct from 1D chains and further linked by hydrogen bonds into the final 3D supramolecular networks. The electrochemical behavior of complexes 1 and 3 were studied by cyclic voltammetry, indicating that the electron transfers in the electrode reaction are irreversible. Meanwhile, complex 2 exhibits significantly red-shifted emission in solid state at room temperature.     

Four complexes with a bulky carboxylate ligand: syntheses,crystal structures,and luminescent properties

Abstract  

Four complexes of 3,3-diphenylpropanoate (L) and 4,4′-bipyridine as auxiliary bridging ligands were synthesized and characterized, namely [Zn(L)₂(4bpy)(EtOH)₂]_∞ (1), [Co(L)₂(4bpy)(EtOH)₂]_∞ (2), [Ni(L)₂(4bpy)(EtOH)₂]_∞ (3), and [Cu(L)₂(4bpy)(H₂O)]_∞ (4) (4bpy = 4,4′-bipyridine). X-ray single-crystal diffraction analyses show that complexes 1–4 all take one-dimensional (1D) fishbone-like structures incorporating bridging 4bpy ligands. The complexes show different supramolecular frameworks interlinked via intermolecular hydrogen bonds, π···π stacking, and/or C–H···π supramolecular interactions. Complex 3 only has a simple one-dimensional fishbone-like chain, whereas complexes 1 and 2 show two-dimensional supramolecular structures by interchain C–H···O hydrogen bonds. Complex 4 is assembled into two-dimensional layers and then an overall three-dimensional framework by a combination of interchain O–H···O hydrogen bonds and C–H···π supramolecular interactions. The luminescent properties of the ligands and their complexes were investigated.     

A series of new oxo-vanadium(IV) complexes with octahedral coordinated vanadium centers

A series of new oxo-vanadium(IV) complexes, [VOCl0.69(OH)0.31 (2,2′-bipy)2]Cl·2H2O (1, 2,2′-bipy?=?2,2′-bipyridine) [(VO)₂Cl₄(4,4'-bipy)₃ (H₂O)₂] (2, 4,4'-bipy?=?4,4'-bipyridine), [VO(ida)(H₂O)]_n (3, H₂ida?=?iminodiacetic acid), and [(VO)₂(oa)₄]_n·4n(H₃O)·n(H₂O) (4, H₂oa?=?oxalic acid), have been synthesized and structurally characterized. 1 contains a [VOCl_0.69(OH)_0.31(2,2′-bipy)₂]⁺ cation, Cl ^– anion and two free H₂O molecules. 2 exhibits a binuclear centrosymmetric moiety built up from two [VOCl₂(4,4'-bipy)(H₂O)] units and one bridging 4,4'-bipy ligand, which provides a rare example of a 4,4'-bipy molecule acting as monodentate ligand. 3 displays a neutral chain [VO(ida)(H₂O)]_n constructed by the linkages of [VO(H₂O)]²⁺ units and ida^2? bridging ligands, while 4 offers the only example of three kinds of oa^2- ligands coexisting within the same anionic chain [(VO)₂(oa)₄^4-]_n. Their spectroscopic properties were investigated, and the magnetic susceptibility of 4 shows antiferromagnetic behavior.     

Synthesis,structure and characterization of new 1D and 2D Ni(II) coordination polymers

Two new Ni(II) coordination polymers, namely [Ni₃(Hsdac)₂(sdac)₂(2,2′-bipy)₂] (1) and [Ni₂(sdac)₂(4,4′-bipy)₂]·2H₂O (2) (sdba = 4,4′-sulfonyldibenzoate, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction analyses. Compound 1 possesses an interesting chain structure. Adjacent chains are further linked through H-bond interactions between Hsdac ligands to give a two-dimensional (2D) supramolecular architecture. Compound 2 displays an unusual 2D polyrotaxane-like network.     

Syntheses, Structure Characterizations and Fluorescent Properties of Two Reduced Molybdenum (V) Phosphates Functionalized by Zinc Coordination Complexes

Two new materials built from reduced molybdenum (V) phosphates as building blocks and zinc coordination complexes as linkers, (H₃O)₂[Zn(2,2′-bpy)]₄[Zn(H₂O)]₂[Zn(HPO₄)₂ (PO₄)₆(MoO₂)₁₂(OH)₆] · 6H₂O (2,2′-bpy=2,2′-bpyridine) 1 and [Zn(phen)(H₂O)₂]₂[Zn(phen) (H₂O)]₂[Zn(H₂O)]₂[Zn(HPO₄)₄ (PO₄)₄(MoO₂)₁₂ (OH)₆] · 7H₂O (phen=1,10-phenanthroline) 2, have been synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction. Compound 1 is a new 3-D structure which constructed from Zn[P₄Mo₆]₂ dimers bonded together with [Zn(2,2′-bpy)] coordination complexes and [Zn(H₂O)] fragments. In compound 2, the Zn[P₄Mo₆]₂ dimeric units are linked by [Zn(phen)(H₂O)] coordination complexes and [Zn(H₂O)] fragments to form a new 2-D framework. The fluorescent activities of compounds 1 and 2 were reported. The crystal data for the two compounds are the following: 1, triclinic, P−1, a=13.036(3) ?, b=13.765(3) ?, c=14.459(3) ?, , Z=1; 2, triclinic, P−1, a=12.708(3) ?, b=14.016(3) ?, c=14.646(3) ?, , Z=1.Dedicated to Professor Michael T. Pope on the occasion of his retirement.     

Synthesis, Characterization and Crystal Structure of a New Cobalt Phosphomolybdate that Contains [(Mo16O32)Co16(H2O)18(PO4)6(HPO4)18] Wheels

A new compound, [Co(H₂O)₆][{Co₂(H₂O)₆}{Co(H₂PO₄)₂}{(PO₄)₆(HPO₄)₁₈(Mo₁₆O₃₂)Co₁₆(H₂O)₁₈}] · 23H₂O (1), has been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, i.r. spectrum, XPS spectrum and single-crystal X-ray diffraction. Compound (1) consists of [(Mo₁₆O₃₂)Co₁₆- (H₂O)₁₈(PO₄)₆(HPO₄)₁₈] wheel-shape clusters as the structural motif, which are covalently linked by [Co₂(H₂O)₆] and [Co(H₂PO₄)₂] fragments to form a two-dimensional layer framework. It is the first time that such wheels have been linked by both mononuclear and dimeric Co^II octahedra. Electronic supplementary material Electronic supplementary material is available for this article at and accessible for authorised users.