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配位化学
POLYHEDRON · 2016 · IF 2.108

Growth, structure, optical and thermal properties of three new organic–inorganic hybrid crystals: (C2H7N4S)3BiCl6·H2O, (C2H7N4S)2BiBr5, and (C2H5N4S)2BiI5

Tongguang Sun,Fei Liang,Xinyuan Zhang,Heng Tu,Zheshuai Lin,Guochun Zhang,Yicheng Wu

Single crystals of three new organic–inorganic hybrid compounds, tri[1-(diaminomethylene)uronium] hexachlorobismuthate ((C 2 H 7 N 4 S) 3 BiCl 6 ·H 2 O, HATU-BCH), bis[1-(diaminomethylene)uronium] pentabromobismuthate, ((C 2 H 7 N 4 S) 2 BiBr 5 , HATU-BB), and bis [3,5-diamino-1,2,4-thiadiazol-2-ium] pentaiodobismuthate ((C 2 H 5 N 4 S) 2 BiI 5 , OHATU-BI), have been successfully grown by slow evaporation method. Their structures were determined by single - crystal X-ray diffraction, in which all anion sublattice structures consist of hexahalobismuthates octahedra with different connection modes involving isolated, shared-corner, and shared-edge. The spectra characters were studied by Infrared and Raman spectra, which interpreted by calculation of the density functional theory (DFT) method and diffuse reflectance spectra. Thermal properties were characterized by thermal gravimetric analysis and differential scanning calorimetry.

研究领域: 材料化学 · 晶体工程 · 配位化学 · 光谱学 · 热分析 · 计算化学
✓ 已验证 DOI 高影响因子
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MICROPOROUS AND MESOPOROUS MATERIALS · 2013 · IF 3.365

Photofunctional hybrid materials with polyoxometalates and benzoate modified mesoporous silica through double functional imidazolium ionic liquid linkage

Jing Cuan,Bing Yan

In our work, we achieve the multi-component assembly of novel kinds of photofunctional hybrid materials with polyoxometalates (POMs, Na 9 EuW 10 O 36 ·32H 2 O (EuW 10 O 36 9 - denoted as EuW10)) and benzoate (4-aminobenzoate, 4-hydroxybenzoate, 4-mercaptobenzoate) modified mesoporous silica through imidazolium ionic liquid (IL, 1-methyl-3-(trimethoxysilylpropyl) compound as double functional linkage. Using Pluronic P123 surfactant as a template, benzoate functionalized SBA-15 mesoporous host is synthesized as result of the co-condensation of tetraethoxysilane (TEOS) and benzoate modified siloxane as precursor. We fabricate POM into the framework of functionalized SBA-15 mesoporous silica with IL. Here IL behaves as double linkage, which both interact with PMO with electrostatic force through ion exchange and form covalent bond to the functionalized SBA-15 mesoporous silica through its alkoxy group after cohydroxylysis and copolycondensation process. Tb 3+ is further introduced into the above hybrid system through coordination bond to carboxylate group of benzoate unit, which can be expected to modify luminescence color and to obtain close white luminescence. The physical characterizations prove these hybrid materials possess high surface area, uniform mesoporous structure, good crystallization and relatively excellent luminescence properties.

研究领域: 无机化学 · 材料化学 · 纳米功能材料 · 光物理学 · 配位化学 · 溶胶-凝胶科学 · 稀土发光材料
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JOURNAL OF SOLID STATE CHEMISTRY · 2022 · IF 3.656

Two transition metal-organic frameworks based on 5-phenyl-isophthalate and N-donor mixed ligands: Structure, magnetic, drug delivery and catalytic properties

Liang Qin,Yan Li,Deyun Ma,Fenglan Liang,Lidian Chen,Chenyang Xie,Jiayong Lin,Yani Pan,Guizhen Li,Fenrou Chen,Peiru Xu,Canlin Hong,Jiaxing Zhu

Two transition metal-based MOFs , {[Ni 2 (pip) 2 (bimb) 1.5 ]·2(H 2 O)} n ( 1 ), and {[Zn(pip)(bimb)]·DMF} n ( 2 ) (pip ​= ​5-phenyl-isophthalate, bimb ​= ​1,4-bis(imidazole-1-ylmethyl)benzene) have been successfully prepared. Complex 1 displays a three-dimensional structure with a 7-connected svk topology with a point symbol of (3 3 ∙4 14 ∙5 3 ∙6). Complex 2 performs a two-dimensional (4,4) sql net with channels of 7.0 ​× ​5.5 ​Å 2 and 10.5 ​× ​4.7 ​Å 2 along the b and c axis, respectively. The magnetic result of 1 shows an antiferromagnetic coupling between the two metal centers. Desolvated 2 adsorbs around 15.25 ​wt% 5-fluorouracil (5-FU). The 5-FU was slowly released without any burst release. The degradation of methyl orange caused by oxidizing sulfate radicals (SO 4− ) in a Fenton-like process has also been explored.

研究领域: 无机化学 · 材料科学 · 药物递送 · 环境催化 · 配位化学
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RSC Advances · 2016 ·Vol. 6 ·期 27 ·22908-22916 · IF 3.289

Palladium(II) and copper(II) chloride complexes bearing bulky α-diimine ligands as catalysts for norbornene vinyl-addition (co)polymerization

Jianwen Tian,Xiaohui He,Jingyin Liu,Xiaodan Deng,Defu Chen

Palladium(II) and copper(II) chloride complexes bearing bulky 9,10-dihydro-9,10-ethanoanthracene-11,12-diimine ligands were synthesized and sufficiently characterized by elemental and spectroscopic analysis along with X-ray diffraction analysis. The X-ray diffraction demonstrated that palladium(II) complexes (C1–C2) and copper(II) complexes (C3–C4) were four-coordinated. All these complexes displayed catalytic activities up to 105 gpolymer molMt−1 h−1 for norbornene vinyl-addition polymerization on treatment with excess methylaluminoxane (MAO). The parameters of the reaction conditions, the type of metals and steric effects of coordinative ligands had influences on the catalytic properties. C2 was selected as a catalyst precursor for the copolymerization of norbornene (NB) with 2-butyloxymethylene norbornene (BN), which exhibited catalytic activities up to 1.1 × 105 gpolymer molPd−1 h−1 and produced copolymers with relatively high molecular weights. The fraction of BN in the copolymer could reach up to 9.8–62.1% by controlling the monomer feed ratio range from 10–80%. The achieved vinyl-addition type poly(NB-co-BN) displayed high thermal stability and was soluble in common organic solvents, such as CHCl3 and THF.

研究领域: 高分子化学 · 配位化学 · 催化化学 · 有机金属化学 · 功能高分子材料
✓ 已验证 DOI 高影响因子
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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 33 ·14103-14107 · IF 3.288

Synthesis, structure and photoluminescence properties of three copper(I) iodide based inorganic–organic hybrid structures with pyrazine derivatives

Chanchan Xu,Le Lv,Dawei Luo,Wei Liu

By using pyrazine derivatives, three different types of copper(I) iodide based inorganic–organic hybrid structures, 1D-CuI(2-mo-pz) (1, 2-mo-pz = 2-methoxy-pyrazine), 2D-CuI(2,3-dm-pz)0.5 (2, 2,3-dm-pz = 2,3-dimethyl-pyrazine), and 2D-Cu2I2(2,5-dm-pz)2 (3, 2,5-dm-pz = 2,5-dimethyl-pyrazine), have been obtained by using a slow-diffusion method. Single crystal and powder X-ray diffraction analyses reveal that these hybrid structures are a one-dimensional (1D) staircase chain based structure, two-dimensional (2D) staircase-chain based structure, and 2D rhomboid dimer based structure, respectively. All of the three compounds show photoluminescence, with the internal quantum yield (IQY) as high as 88.2% for 1. This work provides evidence that for this type of hybrid materials, the structure of the inorganic module could be determined by the selection of the organic ligands and that the substituted group on the organic ligands can influence the luminescence efficiency of the hybrid structures.

研究领域: 无机化学 · 材料化学 · 配位化学 · 光物理 · 功能材料
✓ 已验证 DOI 高影响因子
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JOURNAL OF SOLID STATE CHEMISTRY · 2021 · IF 3.498

Syntheses, structures and Br2 uptake of Cu(I)-bipyrazole frameworks

Sai-Li Zheng,Yonghe He,Xiao-Kang Qiu,Yuan-Hui Zhong,Lai-Hon Chung,Wei-Ming Liao,Jun He

A novel metal-organic framework [CuCN(TMBP)·H 2 O] n ( TCuCN ) has been synthesized by the reaction of 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (TMBP) and CuCN. Its structure was determined by single-crystal X-ray diffraction (SCXRD) analysis and further characterized by power X-ray diffraction (PXRD) analysis, FT-IR spectroscopy and thermogravimetric (TG) analysis. Previously reported structurally analogous TCuCl , TCuBr , TCuI have also been synthesized for Br 2 adsorption comparison. All of these four MOFs exhibited reversible uptake of Br 2 vapor judging by the unchanged PXRD patterns . Among four MOFs, Br 2 -loaded TCuI showed the most uptake amount of Br 2 (15.7 ​wt%), providing the formula to be TCuI ·0.33Br 2 . The different uptake amount of Br 2 for TCuX (X ​= ​CN, Cl, Br, I) should be mainly ascribed to the intermolecular interaction between CuX and Br 2 .

研究领域: 无机化学 · 材料化学 · 配位化学 · 多孔材料 · 气体吸附
✓ 已验证 DOI 高影响因子
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JOURNAL OF SOLID STATE CHEMISTRY · 2017 · IF 2.299

Four thiophene-pyridyl-amide-based ZnII/CdII coordination polymers: Assembly, structures, photocatalytic properties and fluorescent recognition for Fe3+

Xiu-Li Wang,Xiao-Mei Wu,Guo-Cheng Liu,Qiao-Min Li,Hong-Yan Lin,Xiang Wang

By tuning metal ions and combining with different dicarboxylates , four new semi-rigid thiophene-bis-pyridyl-bis-amide-based coordination polymers , namely, [Zn(3-bptpa)(1,3-BDC)]·DMA·2H 2 O ( 1 ), [Zn(3-bptpa)(5-MIP)] ( 2 ), [Cd(3-bptpa)(1,3-BDC)]·2H 2 O ( 3 ) and [Cd(3-bptpa)(5-MIP)]·4H 2 O ( 4 ) (3-bptpa= N,N′ -bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, 1,3-H 2 BDC=1,3-benzenedicarboxylic acid, 5-H 2 MIP=5-methylisophthalic acid, DMA= N,N -dimethylacetamide), were solvothermally/hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analyses, IR spectra , UV–vis diffuse-reflectance spectra (DRS), powder X-ray diffraction (PXRD) and thermal gravimetric analyses (TG). The structural analysis reveals that Zn-complexes 1 and 2 are similar 2D networks. While Cd-complexes 3 and 4 exhibit similar 2-fold interpenetrating 3D α -Po frameworks with the (4 12 ·6 3 ) topology. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of the title complexes have been investigated in detail. Furthermore, the luminescent sensing behaviors for metal cations of 1–4 have been studied, the results indicate that 3 is an excellent fluorescent probe , with high sensitivity, selectivity , and simple regeneration, for environmentally relevant Fe 3+ ions.

研究领域: 无机化学 · 材料化学 · 配位化学 · 环境分析 · 光催化 · 荧光传感
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Journal of Inorganic and Organometallic Polymers and Materials · 2013 ·Vol. 23 ·期 6 ·1492-1500 · IF 1.174

Synthesis, Crystal Structure, Fluorescence and Thermostability of Ni(II), Zn(II), Cd(II) Complexes with Schiff Base 2-Acetylpyridine-d-tryptophan

Zhang Nan,Fan Yu-Hua,Bi Cai-Feng,Zhang Xia,Zhang Peng-Fei,Zhang Zhong-Yu,Li Xin

Three novel transition metal coordination polymers, [Ni(C 18 H 16 N 3 O 2 ) 2 ·2CH 3 OH] n ( 1 ), [Zn(C 18 H 16 N 3 O 2 ) 2 ·4CH 3 OH] n ( 2 ) and [Cd(C 18 H 16 N 3 O 2 ) 2 ·2CH 3 OH] n ( 3 ) (C 18 H 16 N 3 O 2 =2-acetylpyridine- d -tryptophan) were synthesized and characterized by elemental analysis, IR, UV, 1 H NMR and X-ray diffraction single crystal analysis. The analyses of the structures indicate that all three materials crystallize in the tetragonal crystal system, space group P 4 1 2 1 2. They have similar structures; i.e., the Schiff base coordinates in its deprotonated form and behaves as a hexadentate (4N+2O) coordinated ligand to form a distorted octahedron geometry. On the other hand, as a result of the alternate arrangement of chains through N–H···O intermolecular hydrogen bonds interactions, 2-D layers are formed for the three complexes. Furthermore, the luminescent properties and thermal stabilities of the three complexes were investigated.

研究领域: 无机化学 · 配位化学 · 材料化学 · 晶体工程 · 光物理化学
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BIOINORGANIC CHEMISTRY AND APPLICATIONS · 2016 ·Vol. 2016 ·期 1 ·3585781 · IF 1.488

Reversible Oxygenation of α-Amino Acid–Cobalt(II) Complexes

Xincun Zhang,Fan Yue,Hui Li,Yan Huang,Yi Zhang,Hongmei Wen,Jide Wang

We systematically investigated the reversibility, time lapse, and oxygenation-deoxygenation properties of 15 natural α -amino acid–Co(II) complexes through UV-vis spectrophotometer, polarographic oxygen electrode, and DFT calculations, respectively, to explore the relationship between the coordinating structure and reversible oxygenation of α -amino acid–Co(II) complexes. Results revealed that the α -amino acid structure plays a key role in the reversible oxygenation properties of these complexes. The specific configuration of the α -amino acid group affects the electron of Co(II) transfer to the π ⁎ orbit of O 2 ; this phenomenon also favors the reversible formation and dissociation of Co–O 2 bond when O 2 coordinates with Co(II) complexes. Therefore, the co-coordination of amino and carboxyl groups is a determinant of Co complexes to absorb O 2 reversibly. The group adjacent to the α -amino acid unit evidently influences the dioxygen affinity and antioxidation ability of the complexes. The presence of amino (or imino) and hydroxy groups adjacent to the α -amino acid group increases the oxygenation-deoxygenation rate and the number of reversible cycles. Our findings demonstrate a new mechanism to develop reversible oxygenation complexes and to reveal the oxygenation of oxygen carriers.

研究领域: 无机生物化学 · 金属蛋白化学 · 分子生物学 · 配位化学 · 氧化还原生物学
✓ 已验证 DOI 高影响因子
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JOURNAL OF THE CHINESE CHEMICAL SOCIETY · 2017 ·Vol. 64 ·期 4 ·412-419 · IF 0.935

Tetranuclear Zn(II) Complex Based on an Asymmetrical Salamo-Type Chelating Ligand: Synthesis, Structural Characterization, and Fluorescence Property

Xiu-Yan Dong,Sunday Folaranmi Akogun,Wei-Min Zhou,Wen-Kui Dong

A new tetranuclear Zn(II) complex, [{Zn(L)(μ-OAc)Zn(H 2 O)} 2 ], based on an asymmetrical salamo-type bisoxime chelating ligand H 3 L (6-hydroxy-4′-chloro-2,2′-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol) was synthesized and characterized by elemental analyses, differential thermal methods, single-crystal X-ray crystallography, and IR, UV–vis, and fluorescence spectra. The Zn(II) complex crystallizes in the triclinic system, space group P -1 with cell parameters a = 9.0742(6) Å, b = 11.8225(5) Å, c = 12.4182(8) Å, Z = 2, V = 1212.56(12) Å 3 , R 1 = 0.0572, and wR 2 = 0.1734. The environment of the tetranuclear Zn(II) complex is penta-coordinated having a slightly distorted trigonal bipyramidal geometry. Moreover, a 1D chain supramolecular structure is formed along the c -axis by the intermolecular C1–H1B⋯O14 hydrogen bonds; in the same manner, C2–H2C⋯Cg2 functions in the formation of supramolecular structures along the a -axis of the 1D chain. A 2D supramolecular structure along the ac plane extends infinitely under the force of intermolecular hydrogen bonds. Differential scanning calorimetry-thermogravimetry thermal analysis provides evidence of the coordination of Zn(II) atoms to the ligand H 3 L. The Zn(II) complex shows intense photoluminescence with a maximum emission at ~453 nm upon excitation at 360 nm.

研究领域: 无机化学 · 配位化学 · 超分子化学 · 材料化学 · 分析化学 · 物理化学 · 晶体学
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INORGANIC CHEMISTRY · 2019 · IF 4.85

Hexadentate β-Dicarbonyl(bis-catecholamine) Ligands for Efficient Uranyl Cation Decorporation: Thermodynamic and Antioxidant Activity Studies

Qingchun Zhang,Bo Jin,Tian Zheng,Xingyan Tang,Zhicheng Guo,Rufang Peng

The special linear dioxo cation structure of the uranyl cation, which relegates ligand coordination to an equatorial plane perpendicular to the O═U═O vector, poses an unusual challenge for the rational design of efficient chelating agents. Therefore, the planar hexadentate ligand rational design employed in this work incorporates two bidentate catecholamine (CAM) chelating moieties and a flexible linker with a β-dicarbonyl chelating moiety (β-dicarbonyl(CAM)2 ligands). The solution thermodynamics of β-dicarbonyl(CAM)2 with a uranyl cation was investigated by potentiometric and spectrophotometric titrations. The results demonstrated that the pUO22+ values are significantly higher than for the previously reported TMA(2Li-1,2-HOPO)2, and efficient chelation of the uranyl cation was realized by the planar hexadentate β-dicarbonyl(CAM)2. The efficient chelating ability of β-dicarbonyl(CAM)2 was attributed to the presence of the more flexible β-dicarbonyl chelating linker and planar hexadentate structure, which favors the geometric arrangement between ligand and uranyl coordinative preference. Meanwhile, β-dicarbonyl(CAM)2 also exhibits higher antiradical efficiency in comparison to butylated hydroxyanisole. These results indicated that β-dicarbonyl(CAM)2 has potential application prospects as a chelating agent for efficient chelation of a uranyl cation.

研究领域: 无机化学 · 放射化学 · 配位化学 · 药物化学 · 环境毒理学
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INORGANIC CHEMISTRY · 2022 · IF 5.436

Hinokitiol, an Advanced Bidentate Ligand for Uranyl Decorporation

Jingwen Guan,Xiaomei Wang,Peiheng Shi,Lanhua Chen,Bin Chen,Yugang Zhang,Yemeng Chen,Yigong Xu,Zhifang Chai,Shuao Wang,Juan Diwu

Despite the critical role actinide decorporation agents play in the emergency treatment of people in nuclear accidents and other scenarios that may cause internal contamination of actinides, new ligands have seldom been reported in recent decades because the current inventory has been limited to only a handful of functional groups. Therefore, new functional groups are always being urgently sought for the introduction of advanced actinide decorporation agents. Herein, a tropolone derivative, 2-hydroxy-6-(propan-2-yl)cyclohepta-2,4,6-trien-1-one (Hinokitiol or Hino), is proposed to be a promising candidate for this purpose by virtue of its well-demonstrated high membrane permeability and high affinity for metal ions. The coordination stoichiometry of Hino with uranyl is demonstrated to be 3:1 both in an aqueous solution (pH 7.4) and in the solid state. The results of a liquid–liquid extraction experiment further show that Hino exhibits strong chelating ability and selectivity toward uranyl over biological essential metal ions (i.e., Mn2+, Zn2+, Co2+, and Ni2+) with an extraction efficiency of >90.0%. The in vivo uranyl removal efficacies of Hino in kidneys and bone of mice are demonstrated to be 67.0% and 32.3%, respectively. On the basis of the observations described above, it is highly possible that further modification of Hino will lead to a large family of multidentate agents with enhanced uranyl decorporation ability.

研究领域: 无机化学 · 辐射医学 · 毒理学 · 配位化学 · 核应急响应
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