A pair of novel 4-connected homochiral coordination polymers based on proline-tetrazole ligand

A pair of novel 2D homochiral coordination polymers based on proline-tetrazole ligand, namely [Cd((S)-PTZ)₂]_n (1-L) and [Zn((S)-PTZ)₂]_n (2-L), were obtained and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, solid-state CD spectra, single-crystal X-ray crystallography and powder X-ray diffraction. The compounds 1-L and 2-L display 4-connected net and SHG response.     

Solvothermal synthesis and crystal structure of a luminescent 2D copper(I) coordination polymer with a (3,4)-connected net

A novel copper(I) coordination polymer, {[Cu(tpt)(MeCN)](ClO₄)}_∞ (1) (tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine), was synthesized by solvothermal synthesis method and structurally characterized. Single crystal X-ray diffraction showed that 1 consists of a 2D (3,4)-connected network with a unique (5³)₂(5⁴8²) topology. The luminescent properties of 1 in the solid state at ambient temperature were investigated.     

Two new three-dimensional (3,4)-connected lanthanide (III) coordination polymers based on 2-(3-Pyridyl)-1H-imidazole-4, 5-dicarboxylate: Structures and luminescent properties

Two new lanthanide (III) coordination polymers, namely, {[Eu₃(μ₃-HPyIDC)₄]·Cl}_n, (1) and {[Tb₂(μ₃-HPyIDC)₂(μ₂-Ox) (H₂O)₂]·4H₂O}_n (2) (H₃PyIDC = 2-(3-Pyridyl)-1H-4, 5-imidazoledicarboxylic acid; Ox = oxalate), were successfully synthesized under hydro(solvo)thermal conditions and structurally characterized. Compound 1 displays a 3D framework with new (3,4)-connected {4.8.10}₄{4.8⁴.12}₂{4².8⁴} topology built by 3-connected μ₃-HPyIDC⁻ nodes and 4-connected metal ions. Compound 2 exhibits a rare (3,4)-connected dmc topology, in which μ₃-HPyIDC⁻ anions are 3-connected nodes and metal ions are 4-connected nodes. Moreover, the thermal stabilities and luminescence of compounds 1–2 were also investigated.     

Construction of two photoluminescent sulfur-containing cadmium(II) coordination polymers with 4-connected topology based on a methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate ligand

Two new Sulfur-containing Cadmium(II) coordination polymers {[Cd(HL)₂](2H₂O)}_n (1) and {[Cd(L)(bmie)(H₂O)](H₂O)}_n (2) (H₂L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate, and bmie = 1,2-bis(imidazol-1′-yl)ethane) have been successfully constructed and structurally characterized by the single-crystal X-ray diffraction and other characterization techniques, such as elemental analysis, IR spectroscopy and thermogravimetric analysis. Structural analyses reveal that complex 1 exhibits a hydrogen bonded-extended 3D supramolecular structure based upon 4-connected sql layers assembled from single Cd(II) centers as nodes. Complex 2 features a 3D network which can be rationalized as a rare 4-connected cdl topology. It is shown that the H₂L ligand is a suitable building block in constructing coordination polymers with structural diversities. Moreover, solid photoluminescent properties have been investigated.     

A new 2D HgII coordination polymer containing novel coordination mode of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo) ligand, [Hg(μ-bpo)2(N3)2]n: Spectroscopic,thermal, fluorescence and structural studies

A new two-dimensional Hg^II coordination polymer containing 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo) and azide anions, [Hg(μ-bpo)₂(N₃)₂]_n, has been synthesized and characterized by elemental analysis, IR-, ¹H NMR-, ¹³C NMR spectroscopy and structurally determined by X-ray single-crystal diffraction. The thermal stability of compound [Hg(μ-bpo)₂(N₃)₂]_n was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The single-crystal X-ray data shows that ligand bpo is bridged via one pyridyl nitrogen and one oxadiazole nitrogen atom, as a novel coordination mode of the ligand bpo. Furthermore, the ligand and complex are luminescent in the solid state, with emission maxima in the visible light region (λ_max = 470 nm for both bpo and [Hg(μ-bpo)₂(N₃)₂]_n).     

First 3D coordination polymer built from Ho(III) and 2-aminoterephthalate ligand

Novel three-dimensional (3D) coordination polymer {[Ho₂(μ₃-ATA)₂(μ₄-ATA)(H₂O)₄]·2DMF·1/2H₂O}_n (1), built from Ho(III) cations and 2-aminoterephthalate anionic ligands (ATA^2 −) was prepared and studied. The compound 1 contains 1D structural channels with the size 4.1 × 6.8 Å², which propagate along b crystallographic axis. The channels are filled with the solvent molecules. The Ho(III) atom is eight-coordinated with distorted square anti-prismatic geometry. Complex was characterized by single crystal X-ray diffraction, thermogravimetry coupled with simultaneous evolved gas analysis using mass spectrometry (TG/DTG–DTA–EGA), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), solid-state UV–VIS spectroscopy and nitrogen adsorption at 77 K. After the desolvation the 1D structural channels collapse. The process is accompanied by structure transformation, however, according to the TG–DTA–EGA results, the Ho–ATA polymeric framework is stable up to 450 °C.     

Construction of a new 3D Zn(II) coordination polymer with (4,6)-connected topology: Synthesis,structure and luminescence

A new coordination polymer of {[Zn₂(odpa)(IP)]·4H₂O}_n (1) (H₄odpa = 3,3′,4,4′-oxydiphthalic acid and IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline), is reported. The 3D (4,6)-connected {4⁴∙6²∙8⁸∙12}{4⁴∙6²} topology net is formed by IP and odpa ligands in 1. Interestingly, the IP ligand acts as a tridentate mode and extends the resulting 3D feature. The luminescence study indicates that the title compound emits bright red fluorescence.     

A novel heterometallic BaGa coordination polymer based on the bifunctional ligand 2,5-pyridine dicarboxylic acid

The first heterometallic BaGa coordination polymer (CP), namely [Ba₂Ga₂(pydc)₄(OH)₂(H₂O)₂]·3H₂O (1) (H₂pydc = 2.5-pyridine dicarboxylic acid), has been successfully synthesized by the reaction of the bifunctional ligand H₂pydc, BaCl₂·2H₂O and Ga₂O₃ under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that compound 1 features a three-dimensional (3D) network structure constructed from Ga₂(OH)₂ dimers incorporated Ba-pydc skeletons. Luminescence measurements showed that 1 exhibited strong emission band centered at 412 nm ascribed to the emission of ligand-to-ligand charge transfer, which was confirmed by theoretical studies.     

A lamella 2D silver(I) coordination polymer constructed from in situ generated 2-mercaptobenzoic acid

The reaction of Ag₂O and 2,2′-dithiodibenzoic acid (dtba) under ultrasonic condition gave rise to a novel metal–organic coordination polymer [Ag₄(2-mba)₂·(H₂O)₂]_n (1) (2-H₂mba = 2-mercaptobenzoic acid) involving in situ generated 2-mba ligand. Complex 1 shows a lamella 2D structure with a 6³-hcb net which is comprised of fused Ag₆ hexagonal rings. Moreover, 1 exhibits photoluminescence maximized at 468 nm upon 330 nm excitation at room temperature, which may be assigned to a ligand-to-metal charge transfer (LMCT) transition. Semiconducting behavior was also measured at room temperature with σ value of 3.24 × 10^?5 S cm^?1.     

Thermal decomposition of Cu(II)-bis(8-hydroxy-5-quinolyl)methane coordination polymer

The volatile products formed when the coordination polymer of copper(II) and bis-(8-hydroxy-5-quinolyl)methane was heated in vacuum at elevated preselected temperatures were examined. The amount of weight loss at each temperature was determined with a recording thermal balance at each fixed temperature. Infrared spectrophotometry was used to aid in the identification of the major volatile component. A sample was pyrolyzed directly into the mass spectrometer. The results show that the volatile product is for the most part the organic ligand bis(8-hydroxy-5-quinolyl)methane and not derivatives of the copper complex or fragments of the ligand. The mechanism for the decomposition previously proposed is supported.     

Reversible photoluminescence switch: A stair-step Cu4I4 coordination polymer based on a dithioether ligand

A two-dimensional network stair-step Cu₄I₄ coordination polymer (1) based on 1,4-bis((methylthio)propanoyl)piperazine was prepared. No emission was observed from 1 (off state), while a heated sample (2) of 1 emitted a strong green light (on state). Conversion between 1 and 2 was reversible upon removal of acetonitrile or exposure of 2 to acetonitrile.     

Blue emission of a 2D non-interpenetrated zinc coordination polymer constructed through saturated fatty acid ligand

We report a new non-interpenetrated 2D zinc coordination polymer, [Zn(AA)(BPHY)]_n (1) (H₂AA = adipic acid, BPHY = 1,2-bis(4-pyridyl)hydrazine), which is a mixed ligand complex. The solid-state sample of 1 exhibits tunable blue emission excited by UV light with the wavelengths from 320 nm to 380 nm. The luminescent mechanism of 1 has been studied by theoretical calculation.     

4-(5-氨基-6-羟基-2-苯并噁唑基)苯甲酸的合成

系统地研究了AB型新单体：4-(5-氨基-6-羟基-2-苯并口恶唑基)苯甲酸（ABA）的合成方法以及产品析出时pH值条件对其分子形态及红外吸收的影响。以4-(5-氨基-6-羟基-2-苯并口恶 唑基)苯甲酸甲酯（MAB）为原料,60～100 ℃于碳酸钾水溶液中水解反应至溶液澄清,用还原性弱酸性盐的水液在pH值6.0析出结晶、制得纯度99.5%以上高质量的新单体、经FT-IR归属剖析确认为游离的酸式单体ABA,收率达85%;具有过程工艺简便,单体稳定性优异、且无残留DMF阻聚杂质以及聚合操作安全等特点,在制备聚合级AB型PBO单体中取得新进展。     

Synthesis,crystal structure and desulfurization properties of zig-zag 1D coordination polymer of copper(II) containing 4-methoxybenzoic acid ligand

ABSTRACT

Combustion of fuels containing organosulfur compounds has resulted in the emission of sulfur oxides (SO_x) into the atmosphere, therefore, causing serious environmental and health hazards. Herein, slightly distorted octahedral zig-zag 1D coordination polymer of copper(II) [Cu(4-mba)₂(H₂O)₃] was synthesized by reacting copper sulfate pentahydrate with a carboxylate-containing ligand (H-4mba?=?4-methoxybenzoic acid) and employed for sulfur compound uptake. The ligand coordinates to the copper(II) atom via two pairs of deprotonated ligating atoms (carboxylate oxygens) and two water molecules. Structural characterization also reveals that interplay of O–H···O, N–H···O, C-H···O and C–H···π interactions between lattice and coordinated water and ligands significantly contribute to the crystal packing leading to the formation and strengthening of three-dimensional supramolecular assembly. The complex, [Cu(4-mba)₂(H₂O)₃], show potential for desulfurization of fuel with an observed adsorption capacity of 9.6?mg/g at 32°C for 6?h. DFT calculations further revealed a transfer of electron sulfur-containing compounds and the complex, [Cu(4-mba)₂(H₂O)₃], thus leading to a stronger pi–pi interaction.     

Syntheses,structures and properties of novel d10 coordination polymers based on 4-[(1H-imidazol-4-yl)methylamino]benzoic acid ligand

Complete and partial deprotonation of new ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H₂L) under hydrothermal conditions lead to the formation of two novel coordination polymers [ZnL]_n (1) and [Ag(HL)]_n (2). Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework with (4 · 6²)₂(4² · 6¹⁰ · 8³) topology, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions. Both 1 and 2 show remarkable thermal stability and complex 1 was found to show strong blue luminescence with emission maxima at 381 nm upon excitation at 347 nm in the solid state at room temperature.     

A silver(I) ion mediated one-dimensional helical coordination polymer from 1,3-bis(2-pyridylethynyl)-2-methylbenzene

Reaction of 1,3-bis(2-pyridylethynyl)-2-methylbenzene with silver(I) nitrate affords an one-dimensional helical coordination polymer in high yield. The structure of the polymer was confirmed by X-ray crystallography.     

N~2,N~5-双[4-（环氧乙烷-2-基甲氧基）苯基]呋喃-2,5-二甲酰胺的制备及其固化活性研究

以生物基来源的单体FDCA(2,5-呋喃二甲酸)为初始原料,制备了绿色环保的生物基环氧单体N~2,N~5-双[4-(环氧乙烷-2-基甲氧基)苯基]呋喃-2,5-二甲酰胺。通过~1H-NMR(核磁氢谱)、~(13)C-NMR(核磁碳谱)、FT-IR(傅里叶变换红外光谱)和TOF(飞行时间质谱)对制备的生物基环氧的化学结构进行了表征,利用DSC(差示扫描量热仪)在不同的升温速率条件下对其热固化性能进行了研究,然后用Kissinger和Ozawa法对其固化反应的活化能进行了计算。研究结果表明:通过本试验方法可制备该单体,且纯度很高;与传统的双酚A型环氧树脂(DGEBA)相比,在升温速率相同的条件下,其固化峰值温度比双酚A型环氧树脂要低约40℃,但其固化能为137 kJ/mol,而传统的双酚A型环氧树脂的固化活化能为90 kJ/mol。     

Synthesis,structure and properties of a novel 3D pentanuclear [Zn5(OH)2]8 + cluster-based (3,4,11)-connected coordination polymer

A novel coordination polymer based on the multidentate N-donor ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3′-tmbpt) and 1,2,4,5-benzenetetracarboxylate anion (btec), namely, [Zn₅(3,3′-tmbpt)(btec)₂(OH)₂] (1), has been synthesized hydrothermally. Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn₅(OH)₂]^8 + cluster. The optical band gap and photoluminescent property of compound 1 have been studied.     

Blue-green photoluminescent 5- and 10-connected metal 5-(4′-carboxy-phenyl)tetrazolate coordination polymers

Hydrothermal reaction of Zn/Cd salts, NaN₃ and 4-cyanobenzoic acid via in situ [2 + 3] cycloaddition generated two blue-green photoluminescent coordination polymers [Zn(cptta)(H₂O)] (1) and [Cd(cptta)(H₂O)] (2) (H₂cptta = 5-(4′-carboxy-phenyl)tetrazole). When only metal ions are considered as nodes, 1 shows rare 5-connected Shubnikov plane topological type and 2 has unprecedented 10-connected {3¹².4²⁴.5⁹} topological type.