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1.
采用盐酸羟胺和水合肼的混合物分别对PAN纤维进行改性制备了偕胺肟改性PAN纤维(AO-PAN)和混合改性PAN纤维(M-PAN), 并分别与Fe3+进行配位反应生成两种改性PAN纤维铁配合物(Fe-AO-PAN和Fe-M-PAN). 研究了配位反应的动力学特性及温度和Fe3+初始浓度的影响, 并采用DRS和ESR技术比较了两种不同改性PAN纤维铁配合物对偶氮染料活性红195氧化降解反应的催化性能. 结果表明, 在所设定的温度和浓度范围内, 两种改性PAN纤维与Fe3+之间的配位反应平衡符合Langmuir 和Freundlich 吸附等温模型以及Lagergren准二级动力学方程, 并且AO-PAN比M-PAN更容易与Fe3+发生配位反应. 在相同条件下AO-PAN与Fe3+反应的配合量和反应速率常数均比M-PAN与Fe3+反应的高. 两种配合物对染料的氧化降解反应具有催化作用, 暗态条件下Fe-M-PAN比Fe-AO-PAN表现出更高的催化活性, 而光辐射条件下Fe-AO-PAN的催化活性显著增强.  相似文献   

2.
Two cadmium(II) and two zinc(II) coordination complexes with diverse structural motifs, [Cd2(HL)I3H2O] · H2O ( 1 ), [Cd2(H2L)2(H2O)4] · 2SO4 · 14H2O ( 2 ), [Zn3(L′)2(H2O)6] · 4H2O · 2(NO3) ( 3 ), and [Zn3L'2(H2O)2Cl2] · H2O ( 4 ) [H2L = 1,1‐bis(5‐(pyrid‐2‐yl)‐1,2,4‐triazol‐3‐yl)methane; H2L′ = 1,1‐bis(5‐(pyrid‐2‐yl)‐1,2,4‐triazol‐3‐yl)methanone] were synthesized through a hydrothermal method. These coordination complexes were characterized by single‐crystal X‐ray diffraction, powder X‐ray diffraction (PXRD), FT‐IR spectroscopy, and photo‐luminescent experiments. Single crystal structural analysis revealed that 1 – 4 belong to polynuclear coordination compounds. PXRD analysis of 1 – 4 unambiguously confirmed the purity of the as‐synthesized coordination compounds. It is the first time to synthesize coordination compounds based on H2L′, which reacted from the original material H2L through in‐situ hydrothermal conditions. In addition, photo‐luminescent experiments revealed that 1 – 4 have real‐time sensing effects for benzaldehyde through fluorescence quenching. For 1 – 4 , the photo‐luminescent quenching effect for benzaldehyde was also compared and the coordination complexes 3 and 4 based on H2L′ have higher photo‐luminescent quenching effect than compounds 1 and 2 .  相似文献   

3.
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.  相似文献   

4.
Three coordination complexes, namely, [Zn(btbp)(3‐npa)]n ( 1 ), [Co(btbh)(3‐npa)]n ( 2 ), and {[Co(btbb)(5‐nipa)(H2O)] · H2O}n ( 3 ) (btbp = 1,3‐bis(thiabendazole)propane, btbh = 1,6‐bis(thiabendazole)hexane, btbb = 1,4‐bis(thiabendazole)butane, 3‐H2npa = 3‐nitrophthalic acid and 5‐H2nipa = 5‐nitroisophthalic acid) were synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as by single‐crystal X‐ray diffraction. Complex 1 features a fascinating meso‐helical chain, which is further extended into a 2D supramolecular framework involving π ··· π stacking interactions. Complexes 2 and 3 show dinuclear structures. Complex 2 is further connected through C–H ··· O hydrogen bonding interactions to afford a 2D supramolecular layer, whereas complex 3 is further extended to a rare 2‐nodal (3,4)‐connected supramolecular sheet with a point symbol of {3.42.5.6.7}2{3.82} by O–H ··· O hydrogen bonding interactions. The electrochemical behaviors of the two cobalt complexes 2 and 3 were reported. Moreover, the luminescent properties for 1 and the photocatalytic properties for the complexes were investigated.  相似文献   

5.
The molecular structures of blue dichloro‐tetrakis(acrylamide) cobalt(II), [Co{O‐OC(NH2)CH=CH2}4Cl2] ( 1 ) and pink hexakis(acrylamide)cobalt(II) tetrachlorocobaltate(II), [Co{O‐OC‐(NH2)CH=CH2}6][CoCl4] ( 2 ), characterized by single X‐ray diffraction, IR spectroscopy and elemental analyses, are described. The coordination of CoII in 1 involves a tetragonally distorted octahedral structure with four O‐donor atoms of acrylamide in the equatorial positions and two chloride ions in the apical positions. The second complex 2 in ionic form contains CoII cations surrounded by an octahedral array of O‐coordinated acrylamide ligands, accompanied by a [CoCl4]2? anion.  相似文献   

6.
The heteronuclear d‐f coordination complexes [Er2Zn2(C6H5COO)10(phen)2] (1), [Ho2Zn2(C6H5COO)10(phen)2] ( 2 ), [Pr3Zn6(C6H5COO)21(phen)3] ( 3 ), [ErCd(C6H5COO)5(phen)·H2O] ( 4 ), [Ho2Cd3(C6H5COO)12(phen)2] ( 5 ), [EuCd2(C6H5COO)7(phen)2] ( 6 ) (C6H5COOH = benzoic acid;phen = 1,10‐phenanthroline) were synthesized by hydrothermal methods, and their structures were studied by single‐crystal X‐ray diffraction. Complexes 1 , 2 , 4 , and 5 crystallize in the triclinic space group P$\bar{1}$ and complexes 3 and 6 in the monoclinic space group C2/c. The room temperature IR, UV/Vis/NIR absorption, and emission spectra of the six complexes were determined and assigned. In the visible and NIR regions, the emission spectra of complexes show characteristic bands of corresponding LnIII ions, which are attributed to the sensitization from the d block (Zn/Cd‐ligand section) and ligands. In comparison with isolated LnIII ions, the NIR emission bands of complexes 1 – 5 exhibit shifting, broadening and splitting, which are also present in their UV/Vis/NIR absorption spectra. Thus, the two spectra of complexes can evidence each other.  相似文献   

7.
The synthesis of a new ligand (L1) containing two 1,4,7‐triazacyclononane ([9]aneN3) moieties linked by a 4,5‐dimethylenacridine unit is reported. The binding and fluorescence sensing properties toward Cu2+, Zn2+, Cd2+, and Pb2+ of L1 and receptor L2, composed of two [9]aneN3 macrocycles bridged by a 6,6′′‐dimethylen‐2,2′:6′,2′′‐terpyridine unit, have been studied by coupling potentiometric, UV/Vis absorption, and emission measurements in aqueous media. Both receptors can selectively detect Zn2+ thanks to fluorescence emission enhancement upon metal binding. The analysis of the binding and sensing properties of the Zn2+ complexes toward inorganic anions revealed that the dinuclear Zn2+ complex of L1 selectively binds and senses the triphosphate anion (TP), whereas the mononuclear Zn2+ complex of L2 displays selective recognition of diphosphate (DP). Binding of TP or DP induces emission quenching of the Zn2+ complexes with L1 and L2, respectively. These results are exploited to discuss the role played by pH, number of coordinated metal cations, and binding ability of the bridging units in metal and/or anion coordination and sensing.  相似文献   

8.
The water‐stable 3D lanthanide‐organic framework (Ln‐MOF) {[Eu(bci)(H2O)] · 2H2O}n ( 1 ) [H2bci = bis(2‐carboxyethyl)isocyanurate] was synthesized under hydrothermal conditions. Compound 1 ‐ Eu exhibits a 3D open‐framework connected by Eu–(μ‐O)2–Eu chains and bci ligands. Meanwhile, 1 ‐ Eu exhibits highly efficient luminescent sensing for environmentally relevant Fe3+ and SCN ions through luminescence quenching. These results indicated that it could be utilized as a multi‐responsive luminescence sensor.  相似文献   

9.
A microarray‐chip assay system for the fluorescence detection of phosphate‐containing analytes in aqueous media has been constructed from stimuli‐responsive polymerized poly(diacetylene)‐liposomes for the first time. Proper combination of the liposome components (ZnII‐dipicolylamine for phosphate binding and an amine‐terminated component for anchoring the liposome onto an aldehyde‐derivatized glass plate), has led to a microarray chip that selectively detects pyrophosphate, an important biomarker, over competing anions, such as phosphate and adenosine triphosphate, with nanomolar sensitivity. The chip‐based assay shows advantages, such as high specificity and sensitivity, over solution‐based assays that use the same liposomes, and over known homogeneous molecular sensing systems.  相似文献   

10.
Three 1H‐benzimidazole‐5‐carboxylate (Hbic)‐based coordination polymers, {[Ni(H2O)(Hbic)2] · 2H2O}n ( 1 ), {[Ni(H2O)2(Hbic)2] · 3H2O}n ( 2 ), and {[Co2(H2O)4(Hbic)4] · 4DMF · 3H2O}n ( 3 ) were obtained by reactions of the ligand H2bic and NiII or CoII salts in the presence of different structure directing molecules. They were structurally characterized by single‐crystal X‐ray diffraction, IR spectra, elemental analysis, thermal stability, luminescent, and magnetic measurements. Structural analysis suggests that the three polymers exhibit a 2D (4, 4) layer for 1 and 1D linear double chains for both 2 and 3 due to the variable binding modes and the specific spatial orientation of the Hbic ligand towards the different paramagnetic metal ions, which were further aggregated into different 3D supramolecular architectures by popular hydrogen‐bonding interactions. Weak and comparable antiferromagnetic couplings mediating by Hbic bridge are observed between the neighboring spin carriers for 2 and 3 , respectively. Additionally, complexes 1 – 3 also display different luminescence emissions at room temperature due to the ligand‐to‐metal charge transfer.  相似文献   

11.
Three copper(II) coordination polymers (CuCPs), namely, [Cu0.5(1,4‐bib)(SO4)0.5]n ( 1 ), {[Cu(1,3‐bib)2(H2O)] · SO4 · H2O}n ( 2 ), and [Cu(bpz)(SO4)0.5]n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {412 · 63}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 66‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.  相似文献   

12.
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.  相似文献   

13.
2-Fold interpenetrating 3D framework for selective adsorption of CO2 over CH4 and fluorescence detection of Fe3+ ions and nitroaromatic compounds through fluorescence quenching.  相似文献   

14.
Hydrothermal reaction of the metalloligand {[Co(Pzdc)2] · 2H2O}n ( 1 ) with Ce(NO3)3 · 6H2O yields a heterometallic 3d‐4f coordination compound {[Ce2Co(Pzdc)4(H2O)6] · 2H2O}n ( 2 ) (H2Pzdc = pyrazine 2, 3‐dicarboxylic acid). X‐ray structure determination, IR spectroscopy, elemental analysis, thermogravimetric analysis, and magnetic property for the targets are presented. Compound 1 affords one‐dimensional double zigzag chains. Compound 2 features a three‐dimensional CoII–CeIII herringbone structure, in which the slightly deformational 1 and central CeIII atoms are linked by Pzdc2– spacers, and is further analyzed with {4.62}2{42.62.82}{63}2{65.8}2 topology symbol. Magnetic property analysis reveals that the antiferromagnetic interactions occur in compound 2 due to a long‐range superexchange pathway between adjacent magnetic centers. In addition, the solid state photoluminescence of 2 was investigated.  相似文献   

15.
In this work a 1,2,4‐triazole derivative 1‐(4‐aminobenzyl)‐1,2,4‐triazole (abtz) was utilized, one new cadmium(II) coordination polymer, namely [Cd(abtz)I2]n ( 1 ) was prepared through the powerful solvo‐thermal synthetic strategy. In compound 1 , the abtz building blocks are interlinked through the central CdII ions forming the two‐dimensional (2D) layer coordination framework. Powder X‐ray diffraction (PXRD) characterization also reveals that we have prepared the pure phases of coordination polymer 1 . Optical properties have been determined, which can behave the excellent photo‐luminescent emission of coordination polymer 1 . Photo‐luminescent experiment also reveals that coordination polymer 1 can behave the highly sensitive detection for acetone molecules with high Ksv value (Ksv = 4.12 ×104 L · mol–1) in the recyclable detection fashion. Additionally, coordination polymer 1 also can behave the highly sensitive detection for pollutant dichromate with excellent quenching efficiency Ksv (Ksv = 2.12 × 104 L · mol–1) and low detection limit [38 × 10–3 mM (S/N = 3)]. UV/Vis, photo‐luminescent lifetime, and PXRD patterns also have been determined to analyze the detection mechanism.  相似文献   

16.
New copper(II) complexes of the hydrazone ligands H2salhyhb, H2salhyhp, and H2salhyhh, derived from salicylaldehyde and ω‐hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH‐value of the reaction solution. Acidic conditions lead to the formation of the di‐μ‐phenoxo‐bridged dicationic complex dimers [{Cu(Hsalhyhb)}2]2+ ( 1a ), [{Cu(Hsalhyhp)}2]2+ ( 2a ), and [{Cu(Hsalhyhh)}2]2+ ( 3a ), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = ?399 ( 1a ), ?410 ( 2a ), and ?311 cm?1 ( 3a ). Higher pH‐values resulted in the aggregation of neutral copper ligand fragments to the one‐dimensional coordination polymers [{Cu(salhyhb)}n] ( 1b ), [{Cu(salhyhp)}n] ( 2b ), and [{Cu(salhyhh)}n] ( 3b ). 3b has been examined by means of X‐ray crystallography and represents the first example of a structurally characterized neutral copper(II) N‐salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = ?125 ( 1b ), ?136 ( 2b ), and ?148 cm?1 ( 3b ), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH‐control.  相似文献   

17.
By introducing carboxyl tag to the aromatic ligands system and borrowing the organic template open framework idea, a stable fluorescent Zn metal–organic framework was successfully prepared through a rigid ligand H6L (3,5‐bis‐(3‐carboxyphenoxy)benzoic acid) under hydrothermal conditions. The selectivity and sensitivity of the Zn‐MOF to metal ions and nitro‐aromatic compounds (NACs) were investigated by fluorescence quenching. And the Zn‐MOF showed a high sensibility of nitro‐aromatic compounds (NACs) and Fe3+ ions, especially for 4‐(4‐nitropheny lazo) resorcinol (NPLR). More importantly, the detection limit of the Zn‐MOF for detecting NPLR solution was found to be 1.71 ppb. Moreover, this sensor is remarkable recyclable and is promisingly applied for rapid, on‐site and sensing of explosive residuals.  相似文献   

18.
A luminescent coordination polymer with the overall formula {[Zn(tr2btd)(bpdc)]∙DMF}n (where tr2btd = 4,7-di(1H-1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole; bpdc = 4,4′-biphenyldicarboxylate) was synthesized and characterized by single-crystal and powder X-ray diffraction, thermogravimetric, infrared spectroscopy, and elemental analyses. Luminescent properties of the obtained compound were studied in detail both in the solid state and as a suspension in N,N-dimethylacetamide (DMA). It was found that {[Zn(tr2btd)(bpdc)]∙DMF}n exhibits bright turquoise luminescence with excellent quantum efficiency and demonstrates turn-on fluorescence enhancement effect upon soaking in DMA Al3+ solution. Fluorescence titration experiments were carried out and the detection limit for Al3+ ions was calculated to be 120 nM, which is among the lowest reported values for similar materials. Moreover, compound demonstrated excellent selectivity and reusability, and the mechanism of the response is discussed. These results indicate that {[Zn(tr2btd)(bpdc)]∙DMF}n is a promising probe for sensitive fluorescent Al3+ detection.  相似文献   

19.
Over the past two decades, the development of novel inorganic–organic hybrid porous crystalline materials or metal–organic frameworks (MOFs) using crystal engineering has provoked significant interest due to their potential applications as functional materials. In this context, luminescent MOFs as fluorescence sensors have recently received significant attention for the sensing of ionic species and small molecules. In this work, a new luminescent heterometallic zinc(II)–barium(II)‐based anionic metal–organic framework, namely poly[imidazolium [triaqua(μ6‐benzene‐1,3,5‐tricarboxylato)bariumtrizinc] tetrahydrate], {(C3H4N2)[BaZn3(C9H3O6)3(H2O)3]·4H2O}n ( 1 ), was synthesized under hydrothermal conditions and characterized. Compound 1 presents a three‐dimensional framework with an unprecedented (3,5)‐connected topology of the point symbol (3.92).(33.42.5.93.10), and exhibits `turn‐off' luminescence responses for the Cu2+ and Fe3+ ions in aqueous solution based on significantly different quenching mechanisms.  相似文献   

20.
Summary. The interaction of pyridine-N-oxide (pyNO) and 3-picoline-N-oxide (3picNO) with zinc(II) and cadmium(II) azides afforded complexes with empirical formulae Zn(N3)2(pyNO)(H2O)2, Zn(N3)2(3picNO)2(H2O)2 and Cd(N3)2(3picNO)2(H2O)2. The IR spectra of these complexes are measured and discussed. X-Ray single crystal diffraction showed for the first complex, which should be formulated as {[Zn(N3)2(H2O)2](pyNO)}n, to consist of 1D chains of trans-[Zn(N3)2(H2O)2]n, double end-on (-1,1) azido bridges and noncoordinated pyNO molecules. The other two complexes are isomorphous containing 1D trans-[M(N3)2(H2O)2]n, double (-1,1) azido bridges, and hydrogen bonded noncoordinated 3picNO molecules. Each pyridine-N-oxide molecule forms three hydrogen bonds, whereas the 3-picoline-N-oxides form two hydrogen bonds. The metal centers exhibit distorted octahedral geometry.Received March 5, 2003; accepted May 15, 2003 Published online September 11,2003  相似文献   

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