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Synthesis, Crystal Structure, and Photocatalytic Properties of a Zinc(II) Coordination Polymer Based on 3-Hydroxy-2-pyridinecarboxylic Acid
摘要： The zinc(II) compound, [Zn3(HL)6]n (1) (H2L = 3-hydroxypyridine-2-carboxylic acid) was synthesized by a solvothermal reaction of Zn(NO3)2·6H2O and 3-hydroxypyridine-2-carboxylic acid as raw materials. The structure of complex 1 was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, as well as powder X-ray diffraction. X-ray structure analysis demonstrates that the complex crystallizes in the monoclinic system, space group P21/n. There are three zinc ions in the asymmetric unit, which are either five-coordinate or six-coordinate. The asymmetric units are further bridged by the carboxylate of the organic ligands, featuring a 2D framework. The solid state diffuse-reflectance UV/Vis spectra reveals that complex 1 has semiconducting nature with the energy bandgap (Eg) estimated to be 3.11 eV. The photocatalytic properties of complex 1 in degradation of organic dyes were further investigated. Results showed that the complex could degrade 54 % of the dye methylene blue solution within 120 min under UV irradiation light and reused for five times without the decline of the photocatalytic activity.
关键词： Crystal structure,Photocatalytic properties,Zinc,3-Hydroxypyridine-2-carboxylic acid,Solvothermal reaction,Coordination polymer
更新于2025-11-19 16:56:35
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Ultrasonic-Assisted Synthesis of a Zn(II) Coordination Polymer in Aqueous Media and Its High-Performance Luminescent Sensing for 2,4,6-Trinitrophenol
摘要： A novel Zn(II) coordination polymer based on 5-(3-pyridyl)-1,3,4-oxadiazole-2-thiol (Hpzt), namely [Zn(pzt)2]n or (Zn-CP), was synthesized by two different synthetic methods. The bulk polycrystals and single-crystals of Zn-CP were obtained by the conventional solvothermal method at 90°C. The Zn-CP exhibits a two-dimensional (2D) coordination network that contains the uncoordinated Lewis basic sites within each layer. Interestingly, a simple environmentally friendly sonochemical synthesis of the Zn-CP in an aqueous media could be performed at room temperature. The optimal synthetic conditions were studied. The uniform microplates of Zn-CP were obtained within 30 min with the addition of pyridine, acting as a sized modulator and a deprotonating reagent. The influence of the amount of the modulator and the sonication time on their crystalline size was investigated. Moreover, the Zn-CP suspension in an ethanolic media has been used as a luminescence sensor for the detection of nitroaromatic compounds. It shows highly selective and sensitive sensing of 2,4,6-trinitrophenol (TNP) through the quenching (turn off) process under the UV light. Also, the Zn-CP microplates show the higher dispersibility and more stable suspension than those of bulk products causing an increase of the luminescent sensing performance for TNP.
关键词： 2,sonochemical synthesis,4,Zn(II),Coordination polymer,luminescence,6-trinitrophenol
更新于2025-11-19 16:46:39
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Syntheses, crystal structures, and photocatalytic properties of two zinc(II) coordination polymers based on dicarboxylates and flexible bis(benzimidazole) ligands
摘要： Two new ternary zinc(II) coordination polymers (CPs), catena-(μ2-phthalato)-(μ2-1,1'-hexane-1,6-diylbis(2-methyl-1H-benzimidazole))-zinc (CP 1) and catena-(μ2-phenylene-1,4-diacetato)-(μ2-1,1'-hexane-1,6-diylbis(1H-benzimidazole))-zinc (CP 2) were synthesized via hydrothermal process. CP 1 and CP 2 are named as [Zn(L1)(PA)]n and [Zn(L2)(PDA)]n (L1 = 1,1'-hexane-1,6-diylbis(2-methyl-1H-benzimidazole), L2 = 1,1'-hexane-1,6-diylbis(1H-benzimidazole), H2PA = phthalic acid, H2PDA = 1,4-phenylenediacetic acid)), respectively. Both CPs were characterized by elemental analysis, infrared spectroscopy, single crystal X-ray diffraction analysis. CP 1 possesses a 4-connected 66-dia network, CP 2 displays a 2D hcb layer with point symbol {63}. Luminescence, UV-vis diffuse reflection spectra, and photocatalytic properties of two CPs for the degradation of the methylene blue (MB) dye were investigated. The mechanism of photocatalytic degradation of MB was also suggested.
关键词： Zinc(II),Crystal structure,Bis(benzimidazole),Photocatalytic property,Coordination polymer
更新于2025-11-14 15:28:36
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One-Dimensional Mercury Halide Coordination Polymers Based on A Semi-Rigid N-Donor Ligand: Reversible Structural Transformation
摘要： Four one-dimensional (1D) mercury(II) halide coordination polymers have been synthesized by using a semi-rigid N-donor ligand, 2,2′-(1,4-phenylene)-bis(N-(pyridin-3-yl)acetamide) (1,4-pbpa). While [Hg(1,4-pbpa)Cl2·CH3OH]n, 1, forms a sinusoidal chain, the complexes [Hg(1,4-pbpa)X2]n (X = Cl, 2; Br, 3; I, 4) are helical. The sinusoidal 1 undergoes reversible structural transformation with helical 2 upon removal and uptake of CH3OH, which was accompanied with the conformation adjustment of the 1,4-pbpa ligand from trans anti-anti to trans syn-anti. Pyridyl ring rotation of the 1,4-pbpa ligand that results in the change of the ligand conformation is proposed for the initiation of the structural transformation.
关键词： mercury halide,structural transformation,bis-pyridyl-bis-amide,coordination polymer
更新于2025-11-14 15:13:28
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Tin( <scp>ii</scp> ) thiocyanate Sn(NCS) <sub/>2</sub> – a wide band gap coordination polymer semiconductor with a 2D structure
摘要： Semiconductors based on tin(II) show promising hole-transport characteristics due to the 5s electrons that form the valence band. In this paper, we report the synthesis and comprehensive characterization of tin(II) thiocyanate [Sn(NCS)2] and identify it as a novel transparent coordination polymer semiconductor. The single crystal X-ray analysis reveals covalently-bonded 1D polymeric chains that form a 2D structure through Sn–S tetrel bonds. Density functional theory calculations also confirm the importance of the van der Waals interactions between the 2D sheets. Furthermore, we show that the s character of Sn(II) is maintained at the top of the valence band, resulting in dispersed states with a small hole effective mass. The coordination with NCS ligands also leads to a conduction band which is high in energy, giving rise to a wide band gap and excellent transparency in the visible spectrum. This is the first report on the electronic properties of Sn(NCS)2 which highlights the potential of developing new transparent semiconductors based on thiocyanate coordination polymers.
关键词： hole transport,band gap,tin(II) thiocyanate,transparent,semiconductor,coordination polymer
更新于2025-10-22 19:40:53
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A new insight for photocatalytic hydrogen production by a Cu/Ni based cyanide bridged polymer as a co-catalyst on titania support in glycerol water mixture
摘要： A two dimensional Cu/Ni based coordination polymer (CP-1) $0.7(C2H6O2)$1.6(H2O) (4,4?-dipy ? 1,3-di(4-pyridyl)propane) has been demonstrated as a potential co-catalyst on TiO2 support for hydrogen evolution under UV light. CP-1/TiO2 composite exhibits considerable hydrogen production in comparison with the pristine CP-1 and TiO2 (P25), highlighting that the photocatalytic performance is significantly related with the good separation of photo generated e-/h+ pairs. Different wt. % (2.5, 5 and 7.5%) of CP-1 in CP-1/TiO2 composites were tested for photocatalytic hydrogen production in 5 vol % glycerol/water mixture. The 5 wt % CP-1/TiO2 composite displayed the greatest hydrogen production of 9.2 mmol h-1 g-1. The concealed mechanism is divulged on the behalf of results obtained by cyclic voltammetry, photoluminescence and diffused reflectance/UV-visible studies which demonstrate that upon irradiation of UV light, electrons transfer from TiO2 conduction band to CP-1. CP-1 not only grabs the conduction band electrons of titania but also performes as a co-catalyst to reduce the protons into hydrogen. These results are anticipated to direct the forthcoming advancement in creating proficient, cheap semiconductor photocatalysts for solar hydrogen production.
关键词： Hydrogen,Coordination polymer,Co-catalyst,Photocatalyst,Titanium dioxide
更新于2025-09-23 15:23:52
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Coordination Polymers Based on Organic–Inorganic Hybrid Rigid Rod Comprising a Backbone of Anderson-Evans POMs
摘要： To construct polyoxometalates coordination polymers (PCPs), we prepared two pyridine ligand functionalized Anderson POMs: (TBA)3[MnMo6O18((OCH2)3CN=CH-4-Py)2]·DMF ((TBA)3POM-1, TBA = tetrabutyl ammonium, Py = pyridine) and (TBA)3[MnMo6O18((OCH2)3CN=CH-3-Py)2] ((TBA)3POM-2) via the post-functionalization of (TBA)3[MnMo6O18((OCH2)3CNH2)2] (Anderson-NH2) by 4-pyridinealdehyde and 3-pyridinealdehyde, respectively. They are characterized using X-ray single crystal diffraction, MALDI-TOF MS, ESI MS, FT-IR, UV-Vis and 1H NMR . The self-assembly of (TBA)3POM-1 and [Cu(PPh3)2(CH3CN)2]ClO4 (CuP2) in the mole ratios of 1 : 2 and 1 : 3, both gave the same 1D double chain with the molecular formula of (NBu4)n{[Cu(PPh3)2]2(POM-1)}n (7.5DMF)n (1). On the contrary, the self-assembly of (TBA)3POM-2 and CuP2 in the mole ratio of 1:2 yields a 2D coordination polymer of (TBA)n{[Cu(PPh3)2]2(POM-2)}n·(2DMF)n (2), while that self-assembly process in the mole ratio of 1:3 results in different 2D coordination polymer of {[Cu(PPh3)2]3(POM-2)·(CH3CN)}n·(5CH3CN)n (3). Compounds 1-3 can keep their skeleton structures below 230oC. They exhibit intense green emission (496nm for 1; 537nm for 2; 530nm for 3) by ultra-violet irradiation (327nm for 1; 303nm for 2; 331nm for 3), which can be tentatively ascribed as ILCT with metal perturbation.
关键词： Luminescence,Polyoxometalates,Pyridine,Coordination Polymer,Copper (I)
更新于2025-09-23 15:23:52
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A SHG-active manganese coordination polymer with noncentrosymmetric structure based on achiral carboxyphosphinate ligand
摘要： The hydrothermal reaction of MnSO4 with the achiral 2-carboxyethyl(phenyl)phosphinate ligand (H2L) afforded a 2 D coordination polymer manganese phosphinate, [Mn(HL)2]n (1) (H2L ? 2-carboxyethyl(phenyl) phosphinic acid). It contains two types of dimeric ring motifs, which can generate a layer structure through edge-sharing. The interlayer stacking by C-H … p interactions between the C-H groups of the phenyl rings of HL- and the phenyl rings of the adjacent layers results in its crystallization in a noncentrosymmetric crystal structure with (43)2(46(cid:2)66(cid:2)83) topology. Compound 1 shows a second harmonic generation response that is 0.8 times that of urea. The luminescence spectrum indicates an emission maximum at 457 nm, attributed to an intra-ligand emission state.
关键词： noncentrosymmetric structure,manganese,coordination polymer,Hydrothermal synthesis
更新于2025-09-23 15:23:52
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Five new coordination polymers of s- and d-block metals: Structural diversities, magnetic properties and luminescence
摘要： In order to explore the metal ions-controlled syntheses of coordination polymers (CPs), the temperature and solvent ratio were fixed in the reaction processes. By selecting a series of s- and d-block metal ions, five new CPs, [ZnL0.5(H2O)2]n (1), [CoL0.5(H2O)2]n (2), [Mn(H2L)(H2O)2]n (3), [Ca(H2L)(H2O)2]n (4) and [Ba(H2L)(H2O)2]n (5), have been synthesized by employing a less-investigated oxalamide N,N′-bis(4-phthalic acid) (H4L) ligand. H4L shows very versatile coordination modes and leads to various frameworks, including isomorphous 2D grid-like layer based on M2O2 cores for 1 and 2, isomorphous 4-connected 3D PtS frameworks based on 1D [M(CO2)2]n chains for 3 and 4, and a 2D wave-like layer based on [BaO3]n chains for 5.2 and 3 reveal the antiferromagnetic and ferromagnetic properties, respectively, while 1, 4 and 5 possesses strong solid state luminescence.
关键词： Luminescence,Crystal structure,Crystal engineering,Coordination polymer,Magnetic property
更新于2025-09-23 15:22:29
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A Zn(II)/anthracene coordination polymer showing highly efficient photocatalytic Cr(VI) reduction in aqueous solution
摘要： Reaction of Zn(OAc)2·2H2O with the visible light responsive organic ligand 9,10-bis(4′-pyridylethynyl)-anthracene (BPEA) gave rise to a Zn(II)/anthracene coordination polymer [Zn(OAc)2(BPEA)]n. Compound 1 has a one-dimensional (1D) chain structure in which the binuclear {Zn2(OAc)2} cores are linked by the BPEA ligands using the pyridyl N atoms to give to the 1D ladder-like network. The as-prepared compound 1 shows broad-range visible light absorption and good water stability, which are highly demandable for its application in the photocatalysis. The photocatalytic property of 1 were investigated by reduction of Cr(VI) to Cr(III) in aqueous solution under visible light, which reveals its high efficiency and stability in this photocatalytic process.
关键词： Anthracene-based ligand,Coordination polymer,Photocatalysis,Cr(VI) reduction
更新于2025-09-23 15:22:29