Hydrothermal syntheses,structures and luminescent properties of group IIB metal coordination polymers based on bifunctional 1H-tetrazolate-5-acetic acid ligand

Hydrothermal reaction of 1H-tetrazolate-5-ethyl acetate (Htzea), MCl₂ (M = Zn, Cd) and NaOH at different reaction temperatures produced three new coordination polymers: 2-D layered polymer [Zn(tza)(H₂O)₂]_n 1, and 1-D chained supramolecular isomers 2 and 3 formulated as [Cd(tza)(H₂O)₂]_n (H₂tza = 1H-tetrazolate-5-acetic acid), respectively. In these obtained polymers, tza^2? ligand adopts variable coordination modes: μ₃-κN3:κO1:κO2,N1 and μ₃-κN1:κN3:κO2 for 1, and μ₃-κN2:κN1,O2:κO1,O2 for 2 and 3. The effects of reaction temperature and metal centers on the final polymeric frameworks have been discussed. Polymers 1–3 exhibit blue photoluminescence mainly arising from intraligand transitions of tetrazolate rings in tza^2? ligand.     

Crystal structure and magnetic property of a 3D heterometallic coordination polymer constructed by 3-cyanobenzoate and 3-(5H-tetrazol) benzoate ligands

Hydrothermal reaction of Cd(NO₃)₂, Co(NO₃)₂, Na(3-cba) and NaN₃ yielded a 3D heterometallic coordination polymer, [Cd(μ₅-3-tzba)(μ₂-3-cba)(μ₃-OH)Co(H₂O)]_n·2nH₂O 1 (3-H₂tzba = 3-(5H-tetrazol)benzoic acid and 3-Hcba = 3-cyanobenzoic acid), which was characterized by single-crystal X-ray diffraction. The in situ [2 + 3] cycloaddition reaction of nitrile and azide in presence of Cd(II) salt afforded tetrazolate-based 3-tzba^2? ligand. In 1, metal-oxo chains [Cd(μ₃-OH)Co]_n are linked by 3-tzba^2? in an unprecedented μ₅-κN1:κN2:κN3:κN4:κO1,O2 coordination mode to form 2D layers, which are further pillared by 3-cba^? to generate a 3D open framework encapsulating 1D chiral channels. Variable-temperature magnetic studies show that 1 exhibits antiferromagnetic interactions between Co(II) ions bridged by μ₃-OH group.     

Two new d10 2D layered frameworks based on 1,2,4-triazole bridge: Syntheses,structures, and fluorescence

Two new triazole-bridging d¹⁰ 2D layered frameworks, [Cd(H₂O)₂(Httr)₂](SiF₆) (1), [Zn(ttr)(OAc)] (2) (Httr = 3-amino-1H-1,2,4-triazole), were synthesized with structures and fluorescence characterized. 1 is based on a kind of 16-membered ring with μ₂-1 κN:4 κN coordination mode of Httr and 2 is constructed from the fuse of different 6- and 16-membered rings with μ₃-1 κN:2 κN:4 κN mode of ttr⁻. The hydrogen bondings in 1 and 2 between the anions and ttr connect the 2D layers into 3D supramolecular architectures. The fluorescent studies of compounds 1 and 2 show an important difference, emission at 460 nm in 1 and a dual one at 334 and 462 nm in 2.     

Synthesis and characterization of nickel phosphonopropionate hybrid materials

Hydrothermal reaction of nickel acetate with 3-phosphonopropionic acid and 4,4′-bipyridine resulted in two novel phosphonate compounds Ni(HO₃PC₂H₄COO)(4,4′-bpy)(H₂O) · 0.5(4,4′-bpy) (bpy = bipyridine) (I) and Ni(O₃PC₂H₄COOH)(4,4′-bpy)(H₂O)₃ · H₂O (II). Single-crystal X-ray studies reveal that self-assemblies between the ligands and metal ion result in layer (I) and chain (II) structures. Magnetic measurement of I indicate there are ferromagnetic couplings between adjacent Ni²⁺ ions (C = 1.29 cm³ mol⁻¹ K and θ = 2.25 K).     

Synthesis,structure, and adsorption properties of a three-dimensional porous yttrium–organic coordination network

Deprotonation of 4,4′-biphenyldicarboxylic acid (H₂BPDC) with triethylamine followed by the copolymerization with Y(III) in N,N-dimethylformamide (DMF) at room temperature yields a new three-dimensional (3-D) porous metal–organic coordination network, [Y₂(BPDC)₃(DMF)₂(H₂O)₂]_n · (DMF)_n · (H₂O)_n (1). Compound 1 (C_24.50H₁₉N_1.50O₉Y) crystallizes in the triclinic P-1 space group (a = 8.220 (2), b = 13.998 (4), c = 14.212 (4) Å, α = 111.058 (5)°, β = 90.187 (5)°, γ = 94.318 (5)°, V = 1520.9 (7) ų, and Z = 2). X-ray crystallography reveals that 1 consists of a 3-D framework contained open 1-D channels with the dimension of 5 × 10 Å along the crystallographic a axis. The adsorption measurements show that compound 1 can adsorb N₂, Ar and CO₂ into its pores. The adsorption isotherms for MeOH and H₂O were also measured.     

A 2D brickwall architecture from a double-T-shaped ligand and hybrid coordinatively unsaturated copper: Synthesis,structure, and framework dynamic

A double-T-shaped ligand (H₄BPTC) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, [Cu₂(BPTC)(Im)₄(H₂O)(DMF)]_n (1) (DMF = N,N-dimethylformamide, H₄BPTC = Biphenyl-3,3′,4,4′-tetracarboxylic acid, Im = imidazole), which exhibits an interesting framework dynamic upon de-/resolvation.     

Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis,spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

Monoselenocarboxylate–bridged binuclear complexes of Rh^III and Ir^III, [(Cp1MCl)₂(μ-SeCOAr)₂] (1) (M = Rh or Ir; Cp1 = pentamethylcyclopentadienyl; Ar = Ph, C₆H₄Me–4), have been isolated either by the reaction between [Cp1₂M₂(μ-Cl)₂Cl₂] with KSeCOAr in acetonitrile or by treatment of [Cp1MCl(solvent)₂][PF₆] with KSeCOAr in acetone. The novel binuclear complexes, [Cp1IrCl(μ-SeCOAr)(κ²-SeCOC₆H₃R–)IrCp1] (2) (R = H or Me-4) with ortho-metallation at one of the iridium centres have been isolated following the use of excess AgPF₆. The single crystal structure of [Cp1IrCl(μ-SeCOC₆H₅)(κ²-SeCOC₆H₄–)IrCp1] (2a) exhibits two phenylcarboselenolate moieties situated in syn fashion with respect to the “Ir₂Se₂” plane, one of which leans towards the metal centre in order to undergo ortho-metallation after iridium–chlorine bond dissociation.     

Tunable dual-emissive photoluminescence of a zinc(II) coordination polymer based on tetrazolate-carboxylatate acid and 4,4′-bipyridine mixed organic chromophores

Herein, we presented an in-situ hydrothermally synthesized photoluminescent zinc(II) coordination polymer (Zn–CP), namely [Zn₂(tzeba)₂(bpy)]_n1, in which H₂tzeba = 3-(1-tetrazol-ethyl)benzoic acid, bpy = 4,4′-bipyridine. Compound 1 exhibits ligand-centered photoluminescence (PL) and displays interesting dual emissions based on the excitation of different chromophores from the mixed organic ligands. The PL colors of 1 could be tuned from blue-to-cyan-to-green directly by varying the excitation wavelengths. The PL mechanism has been investigated by the density of states (DOS) and density functional theory (DFT) calculations.     

Synthesis,structure and magnetic properties of a copper molybdate hybrid inorganic/organic solid with a novel 10-connected three-dimensional network topology

Hydrothermal reaction of CuCl₂, MoO₃, and 4,4′-dipyridylketone (4,4′-dpk) afforded green crystals of the mixed metal oxide phase {[Cu₂(MoO₄)₂(4,4′-dpk)(H₂O)]·H₂O}_n (1). According to single-crystal X-ray diffraction, {Cu₂O₂} dimers link into 1-D {Cu₂O₂(μ-H₂O)}_n chains via bridging aqua ligands. These chains form [Cu₂(MoO₄)₂(H₂O)]_n slabs via linkage through tetrahedral molybdate anions. In turn, the copper molybdate slabs are pillared through tethering 4,4′-dpk ligands into a 10-connected three-dimensional lattice with an unprecedented 3¹²4³⁰5²6 topology. Variable temperature magnetic data above 140 K were fit to the Curie–Weiss law, with C = 0.17 cm³ K/mol Cu and Θ = 70 K, indicating likely ferromagnetic coupling within the dinuclear kernels of 1; low temperature data points towards the possibility of interdimer antiferromagnetic interactions.     

Two Mn(II)–Au(I) supramolecular assemblies bonded by coordination,aurophilicity and hydrogen-bonding, π–π interactions and their magnetic properties

Two Mn(II)–Au(I) supramolecular assemblies {{Mn[Au(CN)₂]₂(H₂O)₄} [Au(CN)₂]₂(H₂bpy) · H₂O}(bpy = 4,4′-bipyridine) 1 and {Mn(4,4′-dmbpy) [Au(CN)₂]₂(CH₃OH)} (4,4′-dmbpy = 4,4′-dimethyl-bipyridine) 2 have been synthesized and magnetic properties have been investigated The interplay of aurophilicity, coordination, hydrogen-bonding and π–π interactions in two complexes result in three-dimensional network.     

Polycatenation and photoluminescence of two zinc coordination polymers based on arched and linear mixed ligands

Two polycatenated coordination polymers, {[Zn₃(adc)₃(bpp)₄]₂ · 3H₂O}_n (1) and [Zn(adc)(bphy)]_n (2) (adc = azobenzene-4,4′- dicarboxylate, bpp = 1,3-bis(4-pyridyl)propane, bphy = 1,2-bis(4-pyridyl)hydrazine), have been obtained from Zn(NO₃)₂∙ 6H₂O, linear H₂adc ligand and arched bpp/azpy (azpy = 4,4′-azobispyridine) ligands by hydro(solvo)thermal reactions. Compound 1 presents a 2-D structure catenated from 1-D double ladders (1-D → 2-D polycatenation), while compound 2 displays a 3-D structure catenated from 2-D (4,4) stair-stepping layers (2-D → 3-D polycatenation). Luminescence properties of 1 and 2 have been explored, together with study of photoluminescent mechanism by density of states (DOS) calculation.     

Two new luminescent Cd(II)/Zn(II) metal–organic frameworks for exceptionally selective detection of picric acid explosives

Two new coordination polymers, {[Cd(BIDPT)(oba)]·0.5H₂O}_n (1) and {[Zn(BIDPT)(4,4′-sdb)]·2.25H₂O}_n (2) (BIDPT = 4,4′-bis(imidazol-l-yl)diphenyl thioether, H₂oba = 4,4′-oxydibenzoic acid, 4,4′-H₂sdb = 4,4′-sulfonyldibenzoic acid), have been solvothermally synthesized and characterized. Both 1 and 2 show 2-fold interpenetrating 3D frameworks with {6⁵ ∙ 8} cds and {6⁶} dia topology, respectively. These two coordination polymers show strong luminescence and their luminescence could be quenched by a series of nitro explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitro explosives.     

Template-assisted assembly of porous lanthanide coordination polymers with 2-aminoterephthalic acid

Porous lanthanide coordination polymers, {[Ln₂(atpt)₃(H₂O)₂] · 0.5(4,4′-bpy)(H₂O)}_n [Ln = Eu(1), Gd(2), Yb(3), H₂atpt = 2-aminoterephthalic acid, 4,4′-bpy = 4,4′-bipyridine] were obtained by hydro-solvothermal reaction, in which 4,4′-bpy acts as template. For the first time the nitrogen atom of an atpt ligand coordinates to metal ions in 1–3. The photophysical properties and thermal stability of 1 were investigated.     

Polycatenated (4, 4) lanthanide(III) coordination networks based on apidate: Synthesis,structure and properties

Three rare earth coordination polymers, {[Ln₂(μ₃-ADI)₂(μ₂-ADI)(H₂O)₄]·H₂O}_n (Ln = Tb, 1; Eu, 2; Er, 3; ADI = adipate), which show the inclined interpenetration of (4, 4) nets and bright luminescence, were isolated from H₂PDC-assisted (H₂PDC = pyridine-2,3-dicarboxylatic acid) hydrothermal reactions of H₂ADI and Ln₂O₃.     

Hydrothermal synthesis,crystal structure and magnetic properties of a novel nickel carboxylate–phosphonate with a layered structure

Hydrothermal reactions of N-(phosphonomethyl)proline (H₃L) with nickel sulfate hexahydrate resulted in a novel nickel carboxylate–phosphonate: |H₂O|[Ni₃(O₃PCH₂–NC₄H₇–CO₂)₂(H₂O)₄] (complex 1). Single-crystal X-ray diffraction analysis revealed that complex 1 crystallizes in the triclinic space group P-1 (No. 2), with lattice parameters of a = 10.0167(5) Å, b = 10.3882(5) Å, c = 11.9528(5) Å, α = 90.132(3)°, β = 107.246(3)°, γ = 111.158(3)°, V = 1099.39(9) Å³, and Z = 2. Complex 1 features a 2D layered structure. The structure contains alternating Ni-centered octahedra (Ni(1)O₆, Ni(2)O₅N and Ni(3)O₅N) and O₃PC tetrahedra linked to construct a layer with rhombohedral 12-MRs holes. The cyclopentylamine moieties of H₃L were grafted onto the layer through coordination of CPO₃, CO₂ and (CH₂)₂NCH₂ with central nickel atoms. These layers are stacked in an AA sequence, which results in a one-dimensional channel in the [001] direction. Water molecules are located in these channels. Magnetic studies showed that complex 1 exhibits predominantly paramagnetic behavior.     

A novel three-dimensional cadmium(II) coordination polymer constructed from dinuclear molecular building block,syntheses, structure and photoluminescence property

A novel cadmium(II) coordination polymer, [Cd₂(pzdc)₂(4,4′-bpy)₂]·4H₂O (1) (H₂pzdc = pyrazine-2,3-dicarboxylic acid; 4,4′-bpy = 4,4′-bipyridine), has been synthesized by hydrothermal reaction of Cd(OAC)₂, H₂pzdc and 4,4′-bpy. Single-crystal X-ray diffraction analysis reveals that 1 constructed from dinuclear building blocks has a three-dimensional (3-D) structure with rob topology. Fluorescent measurement of 1 exhibits strong blue-green emission in the solid state at room temperature, and its framework possess remarkable thermal stability.     

A new acylamide MOF showing uncommon ten-fold interpenetration

In this work, we obtained a novel three-dimensional acylamide MOF, namely Zn(L) (BPDC)·H₂O(1, BPDC^2 − = biphenyl-4,4′-dicarboxylate, L = N,N′-diphenyl-terephthalamide) by solvo(hydro)thermal method. This polymer was characterized by single-crystal X-ray diffraction, thermogravimetry and solid-state luminescence analysis. The outstanding structural feature of compound 1 is 4-connected dia net with uncommon 10-fold interpenetration in the [5 + 5] manner.     

Synthesis and characterization of an unprecedented 3D lanthanide coordination polymer assembled by cubane-like clusters and a flexible V-shaped dicarboxylate ligand

A lanthanide coordination polymer based on H₂sfdb ligand, namely [Tb₄(sdbc)₄(phen)₂(μ₃-OH)₄]_n ∙ 1.5nH₂O (1) (H₂sfdb = 4,4′-sulfonyldibenzoic acid, phen = 1,10-phenanthroline) has been hydrothermal synthesized and characterized. Compound 1 exhibits an unprecedented three-dimensional framework that comprised new cubane-like hydroxo clusters [Tb₄(μ₃-OH)₄]^8 + as the nodes and flexible (sfdb)^2 − ligands as the linkers. In 1, (sfdb)^2 − ligands display completely different four kinds of coordination modes. Interestingly, not only the carboxylate groups but also one oxygen atom of sulfonyl group of (sfdb)^2 − ligand are coordinated with Tb^III ions in 1, which is first found in the compounds based on H₂sfdb ligand. The luminescence experiments show that Tb^III compound exhibits the typical Tb^III-centered luminescence.     

Synthesis,crystal structure and third-order non-linear optical properties of two-dimensional supramolecular polymer [Co2(μ2-4,4′- bipy)2(μ2-be)2(be)2]n

Two-dimensional (2D) metal-organic supramolecular polymer [Co₂(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂]_n 1 (4,4′-bipy = 4,4′-bipyridine, be = benzoate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. The 2D structure is built from the linkage of secondary building units of binuclear [Co₂(μ₂-4,4′-bipy)₂(μ₂-be)₂(be)₂] clusters by a mixed connector of 4,4′-bipyridine and benzoate. The third-order non-linear optical (NLO) properties of the 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 8.30 × 10⁻³⁰ esu for 1 in a 2.70 × 10⁻⁴ mol dm⁻³ DMF solution.     

Solvothermal synthesis,crystal structure and photoluminescent property of a novel 3D cadmium(II) coordination polymer containing [Cd5(μ3-OH)2(μ3-OAc)2]6+ cores

A novel 3D coordination polymer, {[Cd₅(μ₃-OAc)₂(μ₂-OAc)₂(μ₃- OH)₂(pam)₂(4,4′-bpy)₂] · CH₃CH₂OH}_n (1) (H₂pam = pamoic acid, HOAc = acetic acid, 4,4′-bpy = 4,4′-bipyridyl), was solvothermally synthesized and characterized by the single crystal X-ray diffraction. The title compound contains unprecedented [Cd₅(μ₃-OH)₂(μ₃-OAc)₂]⁶⁺ pentanuclear building units which are linked through pam and 4,4′-bpy ligands to afford a three-dimensional structure. The infrared spectroscopy, thermal stability and photoluminescence of the complex were studied.