A new (3,4,7)-connected topology framework based on [Cd2(CO2)3O4N2] second building unit

A new 3D coordination polymer [Cd₂(L³)(BTC)(H₂O)] (1) (HL³ = 3,5-bis(pyridin-3-ylmethoxy)benzoic acid, H₃BTC = 1,3,5-benzenetricarboxylic acid), has been isolated under hydrothermal condition and characterized by single-crystal X-ray diffraction. Compound 1 is constructed from Cd₂-based second building units (SBUs) [Cd₂(CO₂)₃O₄N₂] and displays a 3D (3,4,7)-connected net with (4²·6)(4³·6³)(4⁵·6¹¹·8⁵) topology. In addition, the photoluminescent spectra indicate compound 1 may be a good candidate for blue-luminescent materials.     

A novel polyoxometalate chain constructed from sandwich lanthanide-containing polyanion [Ce(PW11O39)2] and sodium ion linker

A novel sandwich-type lanthanide polyoxometalate (NH₄)₂[N(CH₃)₄]₆Na₂[Ce(PW₁₁O₃₉)₂] · 14H₂O (1) has been synthesized and characterized by cyclic voltammetry, IR spectroscopy and single crystal X-ray diffraction. X-ray diffraction result reveals that the sandwich-type polyanions are linked by sodium ions to form a structure of zigzag chains, and the chains are further connected into an extensive two-dimensional (2D) framework depending on hydrogen bond.     

Solvothermal synthesis of a novel mixed valence Cu(I)/Cu(II) complex containing sulphate, malate and 4,4-bipyridine, [CuCu2(mal)(SO4)(bpy)2 · H2O]n. Unique binding mode of the malate anion

The reaction of CuSO₄ · 5H₂O with 4,4^′-bipyridine and malic acid at 140 °C under solvothermal conditions afforded a mixed valence three-dimensional coordination polymer [Cu^ICu^II₂(mal)(SO₄)(bpy)₂ · H₂O]_n, (1). The building unit consists of a Cu²⁺-dimer in which copper centers are bridged by malate and sulphate anions. SO₄²⁻ anion further connects dimeric unit with the Cu¹⁺ center. Building units are linked by 4,4^′-bipyridine ligands to form double chains, that are interconnected into 3D network through additional sulphate bridge.     

A three-dimensional zincic molybdenum (V) phosphate with helical channel: Synthesis,structure, and electrochemical properties

A new reduced zincic molybdophosphate, (H₂bpp)₃[Zn₃Mo₁₂^VO₂₄(OH)₆(H₂O)₂(HPO₄)₆(PO₄)₂]·2H₂O 1 (bpp = 1,3-bis(4-pyridyl)propane) has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group I 41/a c d with a = 31.8033(4) Å, b = 31.8033(4) Å, c = 34.5593(8) Å, V = 34955.0(10) ų, and Z = 16 and exhibits a 4,6-connected 3-D framework with (3².8⁴)(3⁴.4².8³.9⁵.10) topology. The basic building blocks of [Zn(2)(Mo₆P₄)₂] are linked through [Zn(3)O₆] octahedra and [Zn(1)O₄] tetrahedra to construct 1-D chains along four different directions. Such 1-D chains are further connected by [Zn(1)O₄]²⁺ linkers to form a 3-D intricate framework with helical channels occupied by protonated bpp and water molecules. Additionally, the electrochemical property of the 1-CPE has been studied in detail.     

A new helical coordination polymer constructed on flexible dicarboxylate ligand and CdII center: Structure and luminescence

A novel cadmium coordination polymer [Cd₂L₂(bpp)₂]_n (1) (H₂L = 1,3-adamantanediacetic acid and bpp = 1,3-di-4-pyridylpropane) was prepared under hydrothermal condition. The three-dimensional (3D) structure is built from the interlinking lamellars. The Cd^II ions are six- and seven-coordinated and linked by L^2? ligands, which results in the right- and left-handed helical chains. The layers are stacked with each other via bpp to generate a 3D architecture. At room temperature, the complex 1 shows the strong fluorescent emission bands in the solid state.     

[Zn(BDC)(H2O)2]n: a novel blue luminescent coordination polymer constructed from BDC-bridged 1-D chains via interchain hydrogen bonds (BDC = 1,4-benzenedicarboxylate)

A novel coordination polymer [Zn(BDC)(H₂O)₂]_n 1 (where BDC = 1,4-benzenedicarboxylate), has been synthesized and characterized by X-ray diffraction. 1 crystallizes in the monoclinic space group C2/c, a=15.09(2) Å, b=5.058(7) Å, c=12.196(16) Å, β=103.62(2)°, , Z=4. The most striking feature of 1 is that it consists of a high-dimensional network structure constructed from BDC-bridged 1-D chains via interchain hydrogen bonds. The coordination sphere of the zinc(II) ion is a distorted tetrahedron completed by four oxygen atoms from two water molecules and two BDC ligands. BDC adopts the bis-monodentated (syn–anti) coordination mode linking two adjacent zinc(II) ions. 1 shows strong blue photoluminescence as the result of the fluorescence from the intraligand emission excited state.     

Synthesis and crystal structures of two new inorganic–organic hybrid polyoxomolybdate complexes: [Himi]4[{Co(imi)2(H2O)2}Mo7O24] · 4H2O and [Zn(imi)4]2[(imi)2Mo8O26] · 6H2O

The two new inorganic–organic hybrid polyoxomolybdate complexes [Himi]₄[{Co(imi)₂(H₂O)₂}Mo₇O₂₄] · 4H₂O (1) and [Zn(imi)₄]₂[(imi)₂Mo₈O₂₆] · 6H₂O (2) (imi = imidazole) have been prepared by conventional aqueous solution synthesis. Compound 1 consists of heptamolybdate anions [Mo₇O₂₄]⁶⁻ covalently linked by [CoN₂O₄]²⁺ octahedra into one-dimensional zigzag-shaped chains. The zigzag-shaped chains are further linked together via the hydrogen-bonding interactions to form a 2D supramolecular framework. Compound 2 is build up of an imidazole-coordinated octamolybdate anion, two imidazole coordinating zinc cations and lattice water molecules to form a three-dimensional framework via complex hydrogen-bonding.     

Synthesis, crystal structures and photoluminescence of Zn–Ln heterometallic polymers based on pyridine-2,3-dicarboxylic acid

Three new two-dimensional 3d–4f isostructural heterometallic coordination polymers, namely [Ln₂Zn(2,3-pydc)₄(H₂O)₄·4H₂O]_n (Ln = Sm (1), Eu (2), Gd (3), 2,3-pydcH₂ = pyridine-2,3-dicarboxylic acid) have been successfully synthesized by the hydrothermal reactions of Ln₂O₃, Zn(NO₃)₂·6H₂O, H₂pydc and H₂O. X-ray diffraction analyses reveal that they possess a 2D heterometallic framework containing 1D lanthanide chains based on dimeric [Ln(2,3-pydc)₂(H₂O)₂]₂ unit. The Zn(II) ion, which is six-coordinated by four oxygen and two nitrogen atoms from four 2,3-pydc²⁻ ligands, as a bridge, links the lanthanide chains to make the 1D chains further extend into 2D layer framework. Furthermore, the neighboring layers are assembled into three-dimensional supramolecular network through inter-layer O–HO and C–HO hydrogen-bond interactions. In addition, the solid-state luminescent property of complex 2 was investigated.     

A hemidirected 1-D coordination polymer [Pb2(H2O)2(HBTC)2] · 3H2O extended in holodirected 3-D by weak Pb–O interactions

A new complex, [Pb₂(H₂O)₂(HBTC)₂] · 3H₂O (H₃BTC = 1,3,5-Benzenetricarboxylic acid) (1), has been synthesized under hydrothermal condition. The single-crystal analysis shows that 1 consists of 1-D double-chains with Pb(II) six-coordinated by three H₃BTC and one H₂O molecule with the Pb–O bond distances in the range of 2.56–2.76 Å. When the Pb–O bonding limit extends from 2.76 to 2.90 Å, the potential weak bonds of Pb–O can be found and the coordination number of Pb will increase from six to nine. As a result, the coordination geometry of Pb(II) transforms from hemidirected to holodirected and an infinite 3-D framework is obtained by the connection of the double-chains. The IR spectrum and the TGA–DTA curve of 1 are also reported in this paper.     

A CdSO4-like 3-D framework constructed from monosodium substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes

A 6⁵·8 CdSO₄-like 3-D framework [Cu(en)₂]₃[α-AsW₁₁NaO₃₉]·2H₂O (1) constructed by monosodium-substituted Keggin arsenotungstates and copper(II)-ethylenediamine complexes (en = ethylenediamine) has been synthesized by reaction of Na₈[α-HAsW₉O₃₄]·11H₂O, CuCl₂·2H₂O and ethylenediamine under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. Crystal data for 1: C₁₂H₅₂AsCu₃N₁₂NaO₄₁W₁₁, monoclinic, Cc, a = 20.409(9) Å, b = 16.737(8) Å, c = 16.561(7) Å, β = 104.607(7)°, V = 5474(4) Å³, T = 296(2) K; Z = 4, μ = 24.860 mm⁻¹, GOOF = 1.086, R₁ = 0.0284, wR₂ = 0.0759. To the best of our knowledge, 1 represents the first 6⁵·8 CdSO₄-like 3-D monovacant Keggin arsenotungstate derivative in polyoxometalate chemistry.     

A new three-dimensional ruthenium(II) complex via hydrogen bonds: Ru(bpy)2(ox)·4H2O (bpy=2,2′-bipyridine, ox=oxalate ion)

A hydrogen-bonded complex Ru(bpy)₂(OX)·4H₂O has been synthesized. Its structure consists of a unique three-dimensional network in which Ru(bpy)₂(OX)·4H₂O units are alternatively linked by tetracyclic and octacyclic rings. The cyclic voltammogram of the titled compound has been studied.     

Synthesis and structural characterization of an alternating double aquo-bridged and single cyano-bridged polymeric barium–iron complex: {[Ba2(phen)4(H2O)6Fe(CN)6]·Cl·2(phen)·3H2O}n

A new alternating double aquo-bridged and single cyano-bridged polymeric complex {[Ba₂(phen)₄(H₂O)₆Fe(CN)₆]·Cl·2(phen)·3H₂O}_n (1) (phen = 1,10-phenanthroline) has been synthesized and structurally characterized. In the crystal structure the two centrosymmetric [Ba₂(phen)₄(H₂O)₆] units are bridged through two trans CN groups of [Fe(CN)₆]³⁻ ion, which results in the formation of a zig-zag polymeric chain. In each [Ba₂(phen)₄(H₂O)₆] unit, the two Ba centers are joined by double aquo bridges. Both the Ba atoms are 9-coordinated with distorted mono-capped square antiprismatic geometry. An elaborate hydrogen bonding system holds the parallel polymeric chains together.     

Preparation, crystal structure and properties of two novel metal-organic frameworks assembled from pyridine-3,5-dicarboxylic acid N-oxide

Two novel coordination polymers, [Cu(PDCO) · (H₂O)]_n (1) and [Cd(PDCO)(bipy) · (H₂O) · 5H₂O]_n (2), (H₂PDCO = pyridine-3,5-dicarboxylic acid N-oxide, bipy = 4,4′-bipyridine), have been synthesized under hydrothermal conditions, and their structures were determined by single-crystal X-ray diffraction studies. Polymer 1 features a three-dimensional (3D) network with nonequivalent nodes of (6³)₂(6⁹ · 8⁵ · 10) topology. Polymer 2 exhibits one-dimensional (1D) double-stranded chains. The magnetic character of 1 as well as the gas adsorption and luminescent properties of 2 have been investigated.     

A 3D cadmium(II) coordination polymer constructed from new β-diketone-functionalized pyridinecarboxylate and 4,4′-bipyridine ligands

A new cadmium(II) coordination polymer [Cd₂(L)₂(bpy)]_n·nCH₃OH (1) (H₂L = 2-(3-oxo-3-phenylpropionyl)-6-pyridinecarboxylic acid N-oxide, bpy = 4,4′-bipyridine), has been synthesized from the reaction of H₂L, 4,4′-bipyridine with CdSO₄·8/3H₂O. Compound 1 is an exceptional non-interpenetrating three-dimensional framework and contains double helical chains and rare cross bpy configuration. Interestingly, these helical chains can span two different directions on other alternate layers. Compound 1 shows intense photoluminescence at room temperature.     

The hydrothermal synthesis and structure of a one-dimensional Fe(II)molybdophosphate

A new one-dimensional Fe(II)molybdophosphate of the formula, [(C₁₀H₈N₂)H₂]₂[Fe₄^(II)Mo₁₂^(V)(HPO₄)₆(PO₄)₂(H₂O)₈(OH)₆O₂₄]·8H₂O, (1), has been synthesized by employing hydrothermal methods and characterized by single crystal X-ray diffraction. The structure consists of a network of MO₆ (M = Fe, Mo) octahedra and (H)PO₄ tetrahedra linked through their vertices. The connectivity between the polyhedral units gives rise to one-dimensional chains with eight-membered apertures. The hydrogen bonded interactions between the chains form pseudo two-dimensional layers. Extensive hydrogen bonding also exists between the amine molecule, 4,4^′-bipyridine, water molecule and framework oxygen atoms. Crystal data for 1: monoclinic, space group = P2₁ (no. 4), a=12.549(3) (Å), b=23.496(5) (Å), c=14.551(3) (Å), β=114.87(3)°, , and Z=2.     

A new binuclear potassium (І) complex with a novel 1D infinite water chain containing (H2O)12 clusters

A novel 1D infinite water chain made of (H₂O)₁₂ clusters containing two different chair water hexamers is found in the binuclear coordination compound, [K₂(L)₂(phen)₄]·6H₂O (1) (where L = 2,2′-azanediyldibenzoic dianion, phen = 1,10′-phenanthroline), which has been synthesized and structurally characterized by single-crystal X-ray diffraction. The fluorescence spectrum and thermogravimetric analysis (TGA) of the title complex 1 have been also discussed.     

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine

Two novel Zn(II) coordination polymers, [Zn₅(pytpy)₈(fum)₄(H₂O)₄(OH)₂]_n · n(CH₃OH) · 2n(H₂O) (1) and [Zn₃(pytpy)₄ (btc)₂]_n · 2n(H₂O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H₂fum = fumaric acid, H₃btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum²⁻ anions. Complex 2 is a 3D network structure, μ₂-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.     

Synthesis of a fluorescent gold(I) complex with a thiosemicarbazone, [Au2(3-NO2-Hbtsc)4]Cl2 · 2CH3CN

Direct reaction of gold(I) chloride with 3-nitrobenzaldehyde thiosemicarbazone (3-NO₂-Hbtsc) in the presence of triphenylphosphine in acetonitrile has yielded ionic complex, [Au₂(3-NO₂-Hbtsc)₄]Cl₂ · 2CH₃CN (1). It exhibited an intense fluorescence band (λ_em) at 383 nm (λ_ex = 300 nm), and two bands of medium intensity at 413 and 436 nm (λ_ex = 350 nm). Complex 1 represents first example of ionic gold(I) complex with a thiosemicarbazone.     

Synthesis, characterization and luminescent property of a novel zinc(II) 1,2,3,4-tetra(4-pyridyl)thiophene metal–organic framework

A novel metal–organic framework (MOF) [Zn(TPT)(MPDCO)(H₂O)·H₂O]n (TPT = 1,2,3,4-tetra (4-pyridyl)thiophene, MPDCO = 6-methylpyridine-2,4-dicarboxylic acid N-oxide) (1) was obtained via hydrothermal synthesis and characterized by the elemental analysis, IR spectroscopy, TG analysis, luminescent spectroscopy and single-crystal X-ray diffraction analysis. Single-crystal structural analysis reveals that a one-dimensional (1-D) ladderlike MOF is constructed through the mixed ligands, and it is further connected by the intermolecular hydrogen bonds to form a 3-D supramolecular network. Complex 1 exhibits efficient blue luminescence at room temperature, and the framework is stable below 235 °C.     

A 3D Gd–Ag coordination polymer constructed from pyridine-3,5-dicarboxylic acid: Synthesis, crystal structure and magnetic properties

A novel heterometallic coordination polymer, [AgGd(PDC)₂]·2H₂O (1) (H₂PDC = pyridine-3,5-dicarboxylic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermogravimetric analysis and single-crystal X-ray diffraction. Complex 1 features an unusual three-dimensional network structure in which infinite gadolinium-carboxylate chains are linked by [Ag(PDC)₂]³⁻ metalloligands to form a mixed-metal coordination network. Moreover, the luminescent properties and magnetic properties of 1 have also been investigated.