在水热条件下以(E)-4,4'-(乙烯-1,2-二基)双-(3-吡啶基)苯甲酰胺(L)和1,3,5-均苯三甲酸(H3BTC)为混合配体设计合成了一种新型配位聚合物[Co(L)2(HBTC)].X射线单晶衍射结构分析表明,该配合物显示出一维链结构,其中HBTC配体的两个羧基采取双(单齿)-螯合配位模式连接Co原子形成一维链,含N配体悬挂在链的两侧.此外,配合物修饰的碳糊电极具有高效的电催化活性,能够有效的催化Cr(Ⅵ)、亚硝酸钾和溴酸钾的还原以及抗坏血酸的氧化.同时标题配合物还可作为潜在的光催化材料用于降解有机染料刚果红.

A new organic ligand was constructed by linking pyrimidine and tetrazole group through amide bond and used to build POM-based metal–organic complexes that can be used as catalysts for the catalytic oxidation of sulfides and electrochemical sensors.

6-Nitrobenzimidazole ligand was first introduced into polyoxometalate-based metal–organic architecture, and two unique butterfly-like complexes were obtained. Their applications in electrochemical energy storage and electrocatalysis were studied.

By designing and using a new flexible bis(pyrimidine)-bis(amide) ligand H2L [H2L=N,N '-bis(4-pyrimidinecarboxamido)-1,3-propane], two new polyoxometalate (POM)-based metal-organic complexes (MOCs), H-3[Cu-2(L)(2)(PMo12O40)] (1) and [Cu-2(H2L)(2)(beta-Mo8O26)] (2), were synthesized under solvothermal and hydrothermal conditions, respectively. In complexes 1 and 2, metal-organic units and POM anions are linked together to form two distinct 2D structures. The [PMo12O40](3-) (PMo12) anions were used as mu(4)-bridging ligands in complex 1 and linked the 1D [Cu(L)](n) metal-organic chains to form a 2D layered structure. The [beta-Mo8O26](4-) (Mo-8) anions adopted two diverse coordination modes in complex 2 and connected the 1D [Cu(H2L)](n)(2n+) metal-organic chains to generate a 2D grid structure. Complexes 1-2 can serve as electrode materials of supercapacitor and show large specific capacitances, up to 1065 and 956 F g(-1) at current density of 2 A g(-1), respectively, which surpass the parent POM and most of the previous reported POM-based electrode materials, thus demonstrating the important role of introducing metal-organic units in improving capacitive performances. Besides, the electrocatalytic redox activities of complexes 1-2 were also studied, both of them can be used as electrochemical sensors to detect Cr(VI) ions. They possess high sensitivity of 0.537 and 0.455 mu A mu M-1 and low detection limits of 0.16 and 0.33 mu M, which are below the maximum content of Cr(VI) in groundwater required by the WHO.

Two new polyoxometalate (POM)-based metal-organic supramolecular architectures, [Cu(Hpypa)2(PMo12O40)(& mu;2-Cl)] 3H2O (1) and [Co(H2bpap)(& gamma;-Mo8O28)0.5(H2O)2] H2O (2), were successfully synthesized by using two self-designed pyrimidine-amide organic ligands [N-(pyridin-3-ylmethyl)pyrimidine-4-carboxamide (pypa) and N,N & PRIME;-bis(4-pyrimidinecarboxamido)-1,5-pentane (bpap)], as well as Keggin-type POM anions and octamolybdate anions under hydrothermal conditions. Complex 1 is a 1D supramolecular structure containing dinuclear [Cu2(Hpypa)4(PMo12O40)2(& mu;2-Cl)2] units. Complex 2 exhibits a 3D supramolecular framework consisting of 1D [Co(H2bpap)(H2O)2]n4n+ metal-organic chains and free [Mo8O28]8- anions. The supercapacitor performances of complexes 1 and 2 in a three-electrode system were investigated. When the current density is 1 A g-1, 1 and 2 exhibit specific capacitances of 555 and 675 F g-1, respectively. The symmetrical supercapacitor assembled with complex 2 as the electrode modifier exhibits an energy density of 13.4 W h kg-1 with a power density of 450 W kg-1. Capacitance retention remains at 96% after 6500 cycles. At the same time, the electrochemical sensors prepared with complexes 1 and 2 can be used for the determination of Cr(vi)/Fe(iii) ions in aqueous solution with high sensitivity and low detection limit. Two polyoxometalate (POM)-based metal-organic supramolecular architectures based on two new pyrimidine-amide ligands were prepared. Both of them possess high specific capacitance, good sensitivity and low detection limit for Cr(vi) and Fe(iii) ions.

3-Nitrotyrosine (3-NT), an oxidative stress biomarker, is closely associated with various diseases. Thus, rapid and sensitive detection of 3-NT is of great significance for preventing and treating diseases. Herein, we reported a new 3D zinc-based metal-organic framework (Zn-MOF) [Zn(L)(HBTC)] (L = (E)-4,4'-(ethene-1,2-diyl)bis[(N-pyridin-3-yl)benzamide], H3BTC = 1,3,5-benzenetricarboxylic acid), which was structurally characterized by single crystal X-ray diffraction, IR, PXRD and TG. The Zn-MOF can be used as a highly efficient fluorescence sensing material to provide a direct and low-cost method for the rapid detection of 3-NT and shows high sensitivity with a KSV value of 6.596 × 104 M-1, a rapid luminescence response within 24 s, excellent selectivity, high anti-interference ability and good recyclability. It is the first example of a MOF being used to directly detect 3-NT as a luminescence sensor to our knowledge. The sensing mechanism of the Zn-MOF towards 3-NT is discussed in detail, which provides a basis for the rational design of MOF sensing materials and their application in biomarker detection.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Four new Keggin-based complexes derived from bis(pyrazine)–bis(amide) ligands are used to detect multiple analytes (BrO3− NO2−, Cr(vi) and Fe(iii) ions) and adsorb organic dye molecules from aqueous solution.

以具有丰富N/O配位位点的双嘧啶-双酰胺配体为有机配体,以Keggin型多酸阴离子[SiW12 O40]4-为无机配体在水热条件下合成了一个新型三维金属-有机框架[Cu2(4-bpmah)2(SiW12O40)]·12H2O(4-bpmah=N,N'-双(4-嘧啶甲酰胺基)-1,2-环己烷).该配合物是由配体4-bpmah连接二维[Cu2(SiW12O40)]无机层形成的三维多酸基金属-有机框架.标题配合物修饰碳糊工作电极能够电催化亚硝酸钾和溴酸钾的还原.此外,标题配合物修饰的碳布工作电极可作为超级电容器电极材料且具有良好的充放电性能.

In this paper, a kind of electrochemical sensing material with tunable activity and high stability is fabricated from polymolybdate-based metal-organic complex. The polymolybdate-based metal-organic complex: H2Ni (nppa)2(H2O)2[gamma-Mo8O26] (1) is synthesized by introducing a flexible pyrazine-pyridine ligand containing amine groups: N-(pyridin-3-yl)pyrazin-2-amine (nppa) under hydrothermal condition. Complex 1 exhibit 1D chain structure based on polyoxoanions and metal ions. The nppa ligands are decorated on the 1D chain in mono -dentate fashion. Bulk-modified carbon paste electrode (CPE) fabricated by the title complex is used as the working electrode for electrochemically sensing inorganic and organic molecules in aqueous systems. 1-CPE displays electrochemical sensing activity towards BrO3- and ascorbic acid (AA) with low detection limits of 1.22 and 0.76 mu M, respectively. Meanwhile, 1-CPE can achieve tunable electrochemical sensing performance, relying on different catalytic activity of reduction products corresponding to multi-step redox reactions. Additionally, its electrochemical activity can be retained under different acid environment.

Four isostructural Anderson-type POM-based metal–organic complexes derived from a new bis(pyrimidine)-bis(amide) ligand were synthesized, showing multifunctional electrochemical sensing activities and good adsorption performances for organic dyes.

In this research, a kind of molybdotellurate-based metal-organic complexes decorated by flexible ligand with tunable electrochemical sensing performance is prepared: H2{M2(nppa)2(H2O)6(TeMo6O24)}center dot 4H2O [M = Ni (1), Co (2)]. (nppa = N-(pyridin-3-yl)pyrazin-2-amine). In complexes 1 and 2, [TeMo6O24]6- polyoxoanions connect with metal ions to form one-dimensional chain structures, where the nppa ligands are modified with the metal ions in monodentate model. The title complex shows obvious sensing performance for the detection of BrO3- and ascorbic acid (AA), with low detection limits of 6.44 and 0.92 mu M, respectively. Owing to the different catalytic activities of reduction products in multi-step redox process, tunable electrochemical sensing performance is realized.

In this paper, three new polyoxometalates (POM)-based metal-organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane (4-bpmah) H-2[Cu(4-bPrnah)(2)(SiMo12O40)(H2O)(2)]center dot 2H(2)O (1), H[cu(4-bpmah)(2)(PMo12O40(H2O)(2)]center dot 2H(2)O (2) and [Cu(4-bpmah)(H2O)(2)[Cu-2(TeMo6O24 )(H2O)(10)center dot 4H(2)O (3) were synthesized by hydrothermal method. Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural, in which the isolated Keggin-type [SiMo12O40](4-)/[PMo12O40](3-) anions and [Cu(4-bpmah)(2)(H2O)(2)](2n+) units were expanded into 3D supramolecular structures through hydrogen bond interactions. In complex 3, the 1D [Cu(4-bpmah)(H2O)(2)](2n+) metal-organic chains and isolated [Cu-2(TeMo6O24)(H2O)(10)](2n-) units were expanded into a 3D supramolecular framework by the hydrogen bond interactions. In this paper, carbon cloth working electrodes composited by the title complexes (1/CC, 2/CC and 3/CC) were prepared and used as electrodes for supercapacitors. The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied. Furthermore, the electrochemistry and electrocatalytic behaviors of complexes 1-3 bulk-modified carbon paste electrodes (1-CPE, 2-CPE and 3-CPE) toward the reduction of KBrO3, KNO2, Cr(VI), as well as their sensing behaviors on Cr(VI) were investigated. (C) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Three new Anderson-type polyoxometalate (POM)-based metal-organic frameworks (POMOFs) [Co-3(L-1)(TeMo6O24) (H2O)(10)]center dot 8H(2)O (1), [Co-3(L-2)(TeMo6O24)(H2O)10]center dot 8H(2)O (2) and [Cu-3(L-1)(TeMo6O24)(H2O)(10)]center dot 6H(2)O (3) (L-1 = N,N'-bis(4-pyrimidinecarboxamido)-1,2-ethane, L-2 = N,N'-bis(4-pyrimidinecarboxamido)-1,4-butane) were obtained under 90 degrees C aqueous solution for two days. POMOFs 1-3 show fascinating 3D framework structures formed by transition metal linking bis(pyrimidine)-bis(amide) ligands and Anderson-type [TeMo6O24](6-) anions. The carbon paste electrodes bulk-modified by POMOFs 1-3 (1-, 2-, 3-CPEs) have good bifunctional electrocatalytic performance towards the oxidation of ascorbic acid and the reduction of potassium bromate, potassium nitrite and heavy metal ions Cr(VI). 1-, 2-, 3-CPEs can be used as electrochemical sensors for the detection of Cr(VI), the limits of detection (LODs) are 0.389 similar to 0.422 mu M, which are lower than the 1.0 mu M standard set by the WHO. In addition, the adsorption properties of POMOFs 1-3 on organic dyes gentian violet (GV) and methyl orange (MO) were investigated.

A new 3D luminescent coordination polymer (LCP) 1 was synthesized for detecting biomarker 3-nitrotyrosine. By adjusting the reaction conditions, Nano-LCP 1 was synthesized, which has a more lower detection limit compared with LCP 1.

Three new Ni(II)/Cu(II) coordination polymers (CPs), [Ni(L-1)(1.5)(HBTC)(H2O)] (1), [Ni(L-2)(2)(HBTC)].2H(2)O (2) and [Cu-2(L-2)(0.5)(BTC)(mu(3)-OH)].2H(2)O (3) {H3BTC = benzene-1,3,5-tricarboxylic acid, L-1 = (E)-4,4'-(ethene-1,2-diyl)bis[N-(pyridin-3-yl)benzamide] and L-2 = (E)-4,4'-(diazene-1,2-diyl)bis[N-(pyridin-3-yl)benzamide]}, were prepared under hydrothermal and solvothermal conditions by regulating different metals and ligands. The structures of CPs 1-3 were characterized by single crystal X-ray diffraction analyses, infrared spectroscopy (IR) and powder X-ray diffraction (PXRD). CP1 displays a 4-connected 3D topological structure based on [Ni(HBTC)]n chains and [Ni(L-1)(1.5)](n) chains. When L2 was used, CP2 demonstrates a 1D chain structure. CP3 is a 3D metal -organic network with the binodal (3,8)-connected {4.62}(2){4(2).6(22).7.8(3)} topology constructed from {Cu4} clusters and L-2 ligands. The photocatalytic properties and electrochemical behaviors of CPs 1-3 were explored. The effect of solvent on the formation of the title CPs as well as the influence of the central metals and ligands on the structures and properties are discussed.

Two new Keggin-type polyoxometalate (POM)-based metal-organic complexes (MOCs) H3[Cu2(4-dpye)2(PMo12O40)] (1) and H[Cu2(4-Hdpye)2(PMo12O40)(H2O)4]·2H2O (2) were constructed with a new N,N'-bis (4-pyrimidinecarboxamido)-1,2-ethane (4-H2dpye) ligand by the hydrothermal/solvothermal method. Complex 1 was a 2D layered structure constructed from 1D metal-organic chains [Cu(4-dpye)]n and Keggin-type [PMo12O40]3- polyoxoanions. Complex 2 displays a 3D supramolecular framework formed by discrete [PMo12O40]3- polyoxoanions and binuclear metal-organic loops [Cu2(4-Hdpye)2]. The electrocatalytic behaviors of carbon paste electrodes modified by complexes 1 and 2 (1-CPE and 2-CPE) were investigated. The 1-CPE and 2-CPE were used as electrochemical sensors to detect trace Cr(vi), and the low limits of detection (LOD) are 1.27 × 10-7 M for 1 and 1.71 × 10-7 M for 2, which are lower than the maximum allowable concentration of Cr(vi) in drinking water specified by the World Health Organization (WHO). In addition, the performances of complexes 1 and 2 modified carbon cloth electrodes (1-CC and 2-CC) as supercapacitor materials have also been studied. The influence of the structure on electrocatalytic and capacitor performances is discussed.

Four cobalt(II)/zinc(II) metal-organic coordination complexes [Co(Hbtc)(L)]center dot H2O (1), [Co-2(bpt)(OH)(L)]center dot 3H(2)O (2), [Zn-3(btc)(2)(L)(2)(H2O)(4)]center dot 2H(2)O (3), and [Zn-2(bpt)(OH)(L)]center dot 2H(2)O (4) have been synthesized from hydrothermal reaction of cobalt (or zinc) nitrate with the mixed ligands of the naphthalene-bridging amide L (N',N ''-di(pyridin-3-yl)naphthalene-2,6-dicarboxamide) and two kinds of tricarboxylic acids (H(3)btc = 1,3,5-benzenetricarboxylic acid, H(3)bpt = biphenyl-3,5,4'-tricarboxylic acid). Complex 1 shows an interesting 3D coordination framework with 3,5-connected {4(2).6(5).8(3)}{4(2).6} topology, which represents a 2-fold interpenetrating 3D net constructed by 1D [Co(Hbtc)](n) ribbon chains and 1D [Co(L)](n) wave chains. Complexes 2 and 4 exhibit similar unique 3D networks based on the 2D [M-2(bpt)(OH)(L)](n) (M = Co for 2, Zn for 4) layers and mu(2)-bridging L ligands, showing the 3,10-connected {4(10).6(32).8(3)}{4(3)}(2) topology. Complex 3 displays a 2D layered coordination framework with the 3,4-connected {6.8(2)}(2){6(4).8(2)}(2){8} topology, representing an interesting three-fold interpenetrating feature. The diverse framework structures of four cobalt(II)/zinc(II) complexes reveal the influences of different metal ions and tricarboxylic acids on the construction of these coordination frameworks. The fluorescent emission behaviors of 1-4 and the fluorescent sensing efficiencies of 3-4 have been studied. Complexes 3-4 display remarkable fluorescence quenching phenomenons towards Fe3+ ions and CrO42- anions. Moreover, the photocatalytic activities of 1-4 towards degrading dye molecules have also been investigated.

A new 3D metal?organic framework (MOF) derived from the 1D [Mo3O10](n)(2n-) chains and the flexible N,N'-bis(5-methyl-2-pyrazinecarboxamide)-1,2-ethane (bmpae), [Cu(bmpae)(0.5)(Mo3O10)(H2O)]center dot H2O (1) has been hydro-thermally synthesized. Crystal analysis reveals that complex 1 is a 3D polyoxometalate (POM)-based MOF containing the 2D [Cu(bmpae)(0.5)](n)(2n+) metal-organic layers and the 1D inorganic [Mo3O10](n)(2n-) chains. The electrochemical behaviors and electrochemical sensing property of the title complex were studied, and its adsorption capacities towards organic dyes gentian violet (GV) and methylene blue (MB) were also investigated.