December 2021Vol. 40, Issue 12
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ArticleTheoretical Study of Non-heme Mn(V)-oxo Complexes: Formation Mechanism, Electronic Nature, and Hydroxylation ReactivityWEN Zi-Hao, LI Shuang and ZHANG Min-Yi*
Chin. J. Struct. Chem. 2021, 40, 1557-1566 DOI: 10.14102/j.cnki.0254-5861.2011-3209
December 15, 2021
C–H bond activation, non-heme manganese complex, homogeneous catalysis, density functional theory calculations
ABSTRACT
Many non-heme manganese complexes exhibit high reactivity and enantioselectivity for the activation of C–H bonds. Recently, Mn(PDP) complexes (PDP = N,N΄-bis(pyridine-2-ylmethyl)-2,2΄-bipyrrolidine) have been reported to activate C–H bonds selectively in the presence of carboxylic acids. In this study, we performed density functional theory calculations to investigate the formation and hydroxylation mechanisms of Mn(PDP) complexes. Our calculation results showed that Mn(III)(PDP) complexes react with H2O2 and carboxylic acid to form Mn(V)-oxo oxidation intermediate. The main oxidation intermediate, [(PDP)Mn(IV)(O···OC(O)CH3)2-·]2+, was found to have the characteristics of S(Mn) = 3/2 manganese(IV) center antiferromagnetically coupled to a σ*O–O radical, where the O–O bond is not completely broken. Furthermore, [(PDP)Mn(IV)(O···OC(O)CH3)2-·]2+ was shown to have two single electron-accepting orbitals (α Mn-dxy and β σ*O–O) that can simultaneously interact with a doubly occupied electron-donating orbital (σC–H) of substrate. Therefore, [(PDP)Mn(IV)(O···OC(O)CH3)2-·]2+ species can act as a two-electron oxidant for the C−H bond functionalization. As a result, the C−H bond hydroxylation by [(PDP)Mn(IV)(O···OC(O)CH3)2-·]2+ species was a single step. Following the H-abstraction with a low barrier of 4.5 kcal/mol, hydroxyl group would immediately rebound to the radical carbon without barrier. These results provide new insights toward the further development of non-heme manganese catalysts.
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Article3D-QSAR, Molecular Docking and Molecular Dynamics Simulations of 3-Phenylsulfonylaminopyridine Derivatives as Novel PI3Ka Inhibitors
WANG Xiang-Cong, YANG Mao-Cheng, ZHANG Mo-Xuan, HU Yin-Jie, WANG Zhong-Hua* and WU Fan-Hong*
Chin. J. Struct. Chem. 2021, 40, 1567-1585 DOI: 10.14102/j.cnki.0254-5861.2011-3216
December 15, 2021
PI3K inhibitor, 3D-QSAR, molecular docking, molecular dynamics simulation
ABSTRACT
The p110a, catalytic subunit of PI3Ka, was the primary phosphoinositide 3-kinases (PI3Ks) isoform involved in oncogenic RTK signaling and tumorigenesis. In this study, the three-dimensional quantitative structure-activity relationship (3D-QSAR), molecular docking and molecular dynamics simulation were employed to study the binding mode between 3-phenylsulfonylaminopyridine derivatives and PI3Ka. The stable and reliable 3D-QSAR models were constructed based on the application of the comparative molecular field analysis (CoMFA) model (q2 = 0.704, r2 = 0.994) and comparative molecular similarity index analysis (CoMSIA) model (q2 = 0.804, r2 = 0.996). The contour maps illustrated relationship between structure and biological activity. The conformation obtained after MD simulation was more stable than the docked conformation. MD simulation was performed in a more realistic environment, and was much closer to physiological conditions. As a result, five novel PI3Ka inhibitors were designed with better biological activity than the template compound 8. -
ArticleQSAR Study and Molecular Design of Isoquinolone Derivative JNK1 InhibitorsTONG Jian-Bo*, XIAO Xue-Chun, LUO Ding, XU Hai-Yin and WANG Jie
Chin. J. Struct. Chem. 2021, 40, 1586-1594 DOI: 10.14102/j.cnki.0254-5861.2011-3227
December 15, 2021
Topomer CoMFA, HQSAR, molecular docking, isoquinolone derivatives, molecular design
ABSTRACT
JNK1 is a drug target for the treatment of type 2 diabetes, and it plays a key mediator role in metabolic disorders. In this paper, holographic quantitative structure-activity relationship (HQSAR) technology and Topomer comparative molecular field analysis (Topomer CoMFA) technology are used to analyze the quantitative structure-activity relationship (QSAR) of 39 isoquinolone derivatives. The cross validation correlation coefficient (q2) is 0.696 (Topomer CoMFA) and 0.826 (HQSAR), and the non-cross validation correlation coefficient (r2) is 0.935 (Topomer CoMFA) and 0.987 (HQSAR). The results showed that the models have good stability and predictive ability. The Topomer search module was applied to define high contribution fragments in the ZINC database, designing 20 new isoquinolone compounds with theoretically high inhibitory activity. The molecular docking was carried out to explore the interaction between the ligand and target JNK1 protein. This study can provide a theoretical basis for the design of new JNK1 inhibitors. -
ArticleEnhancement of Photocatalytic Degradation of Polyvinyl Chloride Plastic with Fe2O3 Modified AgNbO3 Photocatalyst under Visible-light Irradiation
CHANG Hai-Bo, LIU Jun-Bo*, DONG Zheng, WANG Dan-Dan, XIN Yu, JIANG Zhuo-Lina and TANG Shan-Shan
Chin. J. Struct. Chem. 2021, 40, 1595-1603 DOI: 10.14102/j.cnki.0254-5861.2011-3217
December 15, 2021
photocatalytic degradation, polyvinyl chloride, AgNbO3/Fe2O3
ABSTRACT
The solid-phase photocatalytic degradation of polyvinyl chloride (PVC) plastic with AgNbO3/Fe2O3 is studied under visible-light irradiation. The PVC-(AgNbO3/Fe2O3) samples are characterized by X-ray photoelectron spectroscope (XPS), scanning electron microscope (SEM), gas chromatography (GC), and UV-vis diffusion reflectance spectra (UV-vis DRS). The photocatalytic properties of PVC-(AgNbO3/Fe2O3) samples are systematically investigated. More amounts of generated CO2, greater texture change and higher weight loss rate were exhibited in the system of PVC-(AgNbO3/Fe2O3) than pure PVC film. The weight loss rate is ten times higher than that of pure PVC film, which reaches to 46.53% with optimum amount of 0.5 wt% Fe2O3. Active radicals generate primarily on the surface of Fe2O3 particles, which cause composite plastic decomposition on the PVC-(AgNbO3/Fe2O3) interface and extend into polymer interor. The study provides a new promising way to degrade the plastic waste under visible-light. -
ArticleA New SERS Method Based on Shell-isolated Nanoparticles for Rapidly Quantitative Determination of Hydrogen PeroxideWEN Bao-Ying, SHEN Tai-Long, WU Yuan-Fei and LI Jian-Feng*
Chin. J. Struct. Chem. 2021, 40, 1604-1610 DOI: 10.14102/j.cnki.0254-5861.2011-3210
December 15, 2021
hydrogen peroxide, surface enhanced Raman spectroscopy, shell-isolated nanoparticles, ratiometric, glucose
ABSTRACT
Hydrogen peroxide (H2O2) is an important chemical substance produced in the metabolic process of organisms. Excess or less production could lead to serious effects on the body. Therefore, the development of advanced technology to accurately detect the content of H2O2 is of great significance. Herein, we developed a new ratiometric SERS nanoprobe based on shell-isolated nanoparticles (SHINs) for rapidly quantitative detection of H2O2. Because of the small Raman cross-section of H2O2, the ratiometric nanoprobe is an effective method for indirect detection of H2O2, which is designed based on the reaction of p-mercaptophenylboric acid (MPB) with H2O2 to form p-mercaptophenol (MP). Meanwhile, the nanoprobe was used to achieve quantitative detection of H2O2 and applied in quantitative detection of actual sample¾glucose, whose linear correlation coefficient could reach 0.9947 and 0.9812, respectively. This method expands the application of SERS technology, especially provides a reference for the detection of molecules with small Raman cross-section. -
ArticleSynthesis and Characterization of Polyimides Based on Twisted Non-coplanar Backbone Containing IndolocarbazoleWANG Ting, SU Yu-Miao, CHEN Feng and LI Wen-Mu*
Chin. J. Struct. Chem. 2021, 40, 1611-1620 DOI: 10.14102/j.cnki.0254-5861.2011-3212
December 15, 2021
polyimides, indolocarbazole, thermal stability; DOI: 10.14102/j.cnki.0254-5861.2011-3212
ABSTRACT
A diamine monomer (4,4΄-(((5,11-dihydroindolo[3,2-b]carbazole-6,12-diyl)bis(4,1-phenyl-ene))bis(oxy))dianiline) containing a rigid conjugated indolocarbazole was designed and synthesized through a three-step reaction. A series of high-performance functional polyimides were prepared through simple condensation polymerization of the monomer with different industrial dianhydrides 6FDA, BTDA and ODPA, respectively, which exhibit superior thermal stability, good solubility in polar organic solvents and good mechanical properties. The glass transition temperature (Tg) is above 334 °C, and the 5% weight loss temperature (Td5%) of polyimides under nitrogen atmosphere falls in the range of 502~526 °C. The tensile strength and tensile modulus are 49.45~60.08 MPa and 1.4~1.6 GPa, respectively. In addition, the maximum fluorescence emission wavelength of polyimides in the NMP solution (0.02 mg/mL) are around 448 nm with blue light emission and 451 nm as film without significant red shift, which indicates the prepared polyimides process a certain application potential in high-performance flexible polymer optoelectronic devices. -
ArticleLong-term Stable 2D Dion-Jacobson Phase Perovskite Photodiode with Low Dark Current and High On/off RatioGU Hao, CHEN Shan-Ci and ZHENG Qing-Dong*
Chin. J. Struct. Chem. 2021, 40, 1621-1630 DOI: 10.14102/j.cnki.0254-5861.2011-3200
December 15, 2021
two-dimensional perovskite, Dion-Jacobson, photodiode, on/off ratio, stability
ABSTRACT
A two-dimensional (2D) organic-inorganic hybrid perovskite (OIHP) material is considered as a promising candidate for a long-term stable photodetector owing to its outstanding phase and environmental stability. Herein, we demonstrate a perovskite photodiode based on the DJ phase 2D perovskite (PDA)(MA)n-1PbnI3n+1 (where PDA is 1,3-propylenediamine, MA is methylamine, nominal n = 4). The best-performance device exhibits a high detectivity of 4.57 × 1011 Jones, a responsivity of 0.25 A×W−1 at 480 nm, a low dark current density of 9.60 × 10−4 mA×cm−2, and a remarkable on/off ratio of 3.10 × 105. The unencapsulated device can maintain 95% of the initial photocurrent density after 90 days under an ambient atmosphere with relative humidity (RH) of 65%, demonstrating its improved stability than the 3D counterpart. The excellent stability of the photodiode based on 2D perovskite promises its bright commercial application future. -
ArticleA Polyanionic, Quasi-zero-strain and Open-framework K0.76V0.55Nb0.45OPO4 for Sodium-ion BatteriesLIU Jian-Dong-Yong, YU Xu, BAO Jing-Ze and LIN Ying-Xi*
Chin. J. Struct. Chem. 2021, 40, 1631-1638 DOI: 10.14102/j.cnki.0254-5861.2011-3221
December 15, 2021
anode material, sodium-ion batteries, high structural stability, solid solution reaction
ABSTRACT
A carbon-coated K0.76V0.55Nb0.45OPO4 (KVNP@C) polyanion material was successfully synthe- sized by a simple sol-gel method. The KVNP@C possesses a highly stable inorganic open-framework structure, which is hard to be affected by the Na+ intercalation/deintercalation when used as an anode material for sodium-ion batteries (NIBs). The assembled KVNP@C/Na half-cell shows a capacity retention of 81.2% and an average Coulombic efficiency of 99.8% at a current density of 300 mA/g after 1500 cycles. In-situ XRD analysis reveals a single-phase solid solution reaction mechanism with a lattice expansion of 4.76%. This work sheds insights into the quest for developing novel polyanion-based anode materials for sodium-ion batteries. -
ArticleSynthesis, Structural Characterization, Fluorescence Properties and Herbicidal Activity of Bis(substituted salicylaldehyde) Carbohydrazide Dibutyltin ComplexesFENG Yong-Lan, JIANG Wu-Jiu, ZHANG Fu-Xing and KUANG Dai-Zhi*
Chin. J. Struct. Chem. 2021, 40, 1639-1646 DOI: 10.14102/j.cnki.0254-5861.2011-3214
December 15, 2021
bis(substituted salicylaldehyde) carbohydrazide dibutyltin, fluorescence properties, herbicidal activity
ABSTRACT
A series of dibutyltin complexes, (Bu2Sn)2L, [(Bu2Sn)2L]3 and H2LSnBu2, were synthesized by microwave-assisted methanolic solvothermal method, where H4L is [2-(OH)-R-ArCH=NNH]2CX, and X = O, R = 4-NEt2 (T1), 5-Br (T2); X = S, R = H (T3); R = 5-Br (T4). Their structures were characterized by elemental analysis, IR and (1H, 13C)-NMR spectra. The molecular structure of T2 was confirmed by X-ray diffraction. The crystal of T2 belongs to monoclinic system, space group Ia. Five-coordinated distorted triangular bipyramids and six-coordinated distorted octahedral configurations were formed by the coordination of oxygen and nitrogen atoms of ligand with two dibutyltins, thus forming a trimeric hexanuclear butyltin complex by the cross coordination of three units (Bu2Sn)2L with enol imines. The T2 and T4 exhibit fluorescence emission in DMF solvents and DMF-water mixture. The fluorescence intensity of T2-DMF-H2O system decreases almost linearly with the increase of water volume fraction (WVF). The aggregation fluorescence enhancement effect of T4-DMF-H2O solution system increases with the increase of WVF at the range of 0~20% WVF. When WVF is more than 20%, the fluorescence intensity decreases with the increase of WVF. In addition, T1~T4 have broad growth activities on target plants, such as Portulaca oleracea L., Amaranthus spinosus L., Cassia tora L., Brassica campestris L.ssp.chinensis var.utilis Tsen et Lee, and Amaranthus tricolor L., and can be used as a candidate herbicide for further research. -
ArticleSynthesis, Crystal Structure and DFT Calculation of 2-Methoxyimino Phenylacetate Derivatives Containing 1,3,4-Oxadiazole RingREN Hui-Dong, LI Kang-Ming, YI Yang-Jie, WANG Man, YE Jiao* and HU Ai-Xi*
Chin. J. Struct. Chem. 2021, 40, 1647-1654 DOI: 10.14102/j.cnki.0254-5861.2011-3292
December 15, 2021
2-methoxyimino phenylacetate derivatives, synthesis, crystal structure, fungicidal activities, DFT calculation
ABSTRACT
Four novel 2-methoxyimino phenylacetate derivatives containing 1,3,4-oxadiazole ring were designed and synthesized from the key intermediate of Trifloxystrobin or Azoxystrobin via intermediate derivatization and active structure splicing. The chemical structures of the target compounds were confirmed by 1H NMR, 13C NMR and elemental analysis. The crystal structure of methyl (E)-2-(methoxyimino)-2-(2-(((5-((4-methoxyphenoxy)methyl)- 1,3,4-oxadiazol-2-yl)thio)methyl)phenyl)acetate (A1) was determined by single-crystal X-ray diffraction. Compound A1 belongs to triclinic system, space group P with two molecules in each unit cell. The benzene ring plane C(2)–C(3)–C(4)–C(5)–C(6)–C(7) and oxazole ring plane are nearly parallel with the dihedral angle of 6.4°. The benzene ring plane C(12)–C(13)–C(14)–C(15)–C(16)–C(17) and oxazole ring plane are not perpendicular with the dihedral angle of 49.4°. The crystal of compound A1 is stabilized by π-π stacking interactions. The fungicidal activities of the target compounds against four plant pathogenic fungi in vitro were tested, and some of them had good activities. The DFT calculation was carried out to study the structure-activity relationship of the title derivatives using Gasian 09 and Multiwfn 3.6. -
ArticleTwo Polyoxometalate-based Host-guest Compounds: Synthesis, Crystal Structure and Catalytic PerformanceWANG Song-Xia, WANG Sa-Sa, WU Xiao-Yuan, YANG Wen-Bin and LU Can-Zhong*
Chin. J. Struct. Chem. 2021, 40, 1655-1660 DOI: 10.14102/j.cnki.0254-5861.2011-3226
December 15, 2021
polyoxometalates, catalytic oxidation, aniline, nitrosobenzene
ABSTRACT
Two polyoxometalate-based host-guest compounds, (HL1)2(HPW12O40)·~11H2O (1), (HL2)3(PW12O40)·3H2O (2) (L1 = guanine, L2 = 2-(1H-1,2,4-triazol-3-yl)pyridine), were synthesized under hydrothermal conditions and characterized by EA, PXRD, TG, FT-IR and X-ray single-crystal diffraction. Compound 1 crystallizes in trigonal space group P-3 with a = 18.2917(5), b = 18.2917(5), c = 13.5441(5) Å, V = 3924.5(3) Å3, Z = 3, Mr = 3383.26 g/mol, ρcalc = 4.036 g/cm3, F(000) = 4137, μ = 48.532 mm–1, GOOF = 1.062, the final R = 0.0713 and wR = 0.1865 for 9037 observed reflections with I > 2σ(I). Compound 2 crystallizes in trigonal space group R-3 with a = 19.0017(6), b = 19.0017(6), c = 25.6361(9) Å, V = 8016.2(6) Å3, Z = 6, Mr = 3372.45 g/mol, ρcalc = 4.188 g/cm, F(000) = 8886, μ = 47.644 mm–1, GOOF = 1.077, the final R = 0.0380 and wR = 0.0976 for 5904 observed reflections with I > 2σ(I). These two compounds can catalyze selective oxidation of aniline with H2O2 as the oxidant. Under optimal conditions, the conversion of aniline with compound 1 can reach up to 91.25%, and the selectivity of nitrosobenzene is 78.81%. -
ArticleA New Heterometallic 3d-3d Transition Metal Oxo-cluster {CuII6MnIII}: Synthesis, Crystal Structure and Magnetic PropertyWANG Yi-Man, PENG Zhi-Wei, LIAO Jia-Min, LI Ao, LIU Yuan-Yan, ZHANG Jing-Jing, ZHOU Nian, LI Xu-Dong, LI Shu and MENG Wei*
Chin. J. Struct. Chem. 2021, 40, 1661-1667 DOI: 10.14102/j.cnki.0254-5861.2011-3229
December 15, 2021
dipotassium bis(μ-tartrato)-diantimony(III) ligand, heterometallic transition metal oxo-cluster, crystal structure, magnetic study
ABSTRACT
A new transition metal-antimony oxo-cluster based compound has been synthesized in water under room temperature. Its formula is Na6[Cu6MnSb6(μ3-OH)2(OH)(μ4-O)6(tartrate)6]·20H2O (1), where tartrate represents rac-tartaric acid. It was characterized by elemental analysis, infrared spectrum and X-ray single-crystal diffraction. The compound crystallizes in the monoclinic system, space group P21/n. Structural analyses revealed that two Sb3(μ3-O)(tartrate)3 scaffolds sandwich a CuII6MnIII middle layer to form the cluster. In the middle layer, all the seven metal ions lie in an almost regular hexagon, with MnIII ion in the center and six CuII ions along the edges of the hexagon. As a 4-connected node, each cluster is interlinked to its nearest four {Cu6Mn} neighbors through Na+, generating a 3D supramolecular framework. The temperature-dependent magnetic susceptibilities indicated dominating antiferromagnetic interactions in 1 with JCu–Cu = 176.34 and JCu–Mn = –14.44 cm−1. -
ArticleLuminescent Tetra-nuclear Lanthanide-titanium-organic Compound Obtained by the Mixed-ligandCHEN Bing-Ben, ZHAO Wen-Zhuo, CHEN Zi-Bin, WEN Yi-Hang, CHENG Jian-Wen*
Chin. J. Struct. Chem. 2021, 40, 1668-1672 DOI: 10.14102/j.cnki.0254-5861.2011-3220
December 15, 2021
lanthanide, titanium, luminescence
ABSTRACT
A new heterometallic lanthanide-titanium-organic compound: [Eu2Ti2(dip)6(dig)2(H3O)2]·solvent (1, dip = diphenylglycolic acid, dig = diglycolic acid) has been synthesized under solvothermal conditions. Compound 1 contains a tetra-nuclear {Eu2Ti2} unit with the mixed ligands of dip and dig. Compound 1 displays intense red luminescence. Furthermore, the IR, PXRD, UV-vis and TGA spectra were also studied. -
ArticleSelf-assembly Syntheses, Crystal Structures and Quantum Chemistry of Two UO22+ Complexes
TAN Yu-Xinga*, NAN Xiao-Long, TAN Yan-Liang, ZHANG Zhi-Jian and JIANG Wu-Jiu
Chin. J. Struct. Chem. 2021, 40, 1673-1679 DOI: 10.14102/j.cnki.0254-5861.2011-3223
December 15, 2021
UO22+ complexes, synthesis, crystal structure, quantum chemistry
ABSTRACT
Two UO22+ complexes {[C5H4N(O)C=N-N=C(Ph)-(Ph)C=N-N=C(O)-C5H4N]2UO2(CH3OH)} (I) and {[C5H4N(O)C=N-N=C(Ph)-(Ph)C=N-N=C(O)-C5H4N]2UO2(C5H4N(O)C=N-NH2)} (II) were synthesized and characterized by IR, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex I belongs to monoclinic system, space group P21/n with a = 11.7678(4), b = 16.9667(6), c = 14.3051(5) Å, b = 98.918(3)°, Z = 4, V = 2821.64(17) Å3, Dc = 1.837 Mg·m–3, m(MoKα) = 5.805 mm–1, F(000) = 1504, R = 0.0346 and wR = 0.0688. The crystal of complex II is of triclinic system, space group P with a = 11.6417(5), b = 11.7297(5), c = 14.2197(5) Å, α = 71.697(4)°, b = 86.020(3)°, γ = 71.572(4)°, Z = 2, V = 1748.02(12) Å3, Dc = 1.742 Mg·m–3, m(MoKα) = 4.704 mm–1, F(000) = 894, R = 0.0283 and wR = 0.0537. The U1 is a seven-coordinate pentagonal bipyramidal configuration in I and an eight-coordinate hexagonal dipyramidal configuration in II. The thermal stability and quantum chemical calculations of I and II were also investigated. -
ArticleIodine Adsorption Studies of Dipalladium-based Supramolecular CagesLU Hong-Lin, TONG Jin, MA Hong-Weib* and YU Shu-Yan*
Chin. J. Struct. Chem. 2021, 40, 1680-1686 DOI: 10.14102/j.cnki.0254-5861.2011-3271
December 15, 2021
self-assembly, palladium, cages, host-guest, iodine adsorption
ABSTRACT
Four water-soluble cage-like hosts (1·4NO3-: {[(bpy)2Pd2]2L12}(NO3)4, 2·4NO3-: {[(bpy)2Pd2]2L22}(NO3)4, 3·6NO3-: {[(bpy)2Pd2]3L32}(NO3)6 and 4·6NO3-: {[(bpy)2Pd2]3L42}(NO3)6) have been successfully self-assembled by coordinating the flexible amide based polypyrazole ligands (H2L1: N1,N4-di(1H-pyrazol-5-yl)terephthalamide, H2L2: N1,N4-bis(3-methyl-1H-pyrazol-5-yl)-terephthalamide, H3L3: N1,N3,N5-tri(1H-pyrazol-5-yl)benzene-1,3,5-tricarboxamide and H3L4: N1,N3,N5-tris(3-methyl-1H-pyrazol- 5-yl)benzene-1,3,5-tricarboxamide) with dipalladium corners ([(bpy)2Pd2(NO3)2](NO3)2, where bpy = 2,2΄-bipyridine) in aqueous solution. Their structures were characterized by 1H NMR, ESI-MS and single-crystal X-ray diffraction. Notably, all the four supramolecular assemblies are capable of adsorbing iodine molecules via halogen bonds and other supramolecular interactions. -
ArticleStructural Diversity and Magnetic Properties of Two Coordination Polymers Based on 6-(3,5-Dicarboxylphenyl)nicotinic AcidZHAI Li-Jun, TONG Ru, WANG Ci-Bin, SHI Meng-Jie, MO Ya-Nan, CHE Wen-Kai, NIU Yu-Lana* and HU Tuo-Ping*
Chin. J. Struct. Chem. 2021, 40, 1687-1695 DOI: 10.14102/j.cnki.0254-5861.2011-3354
December 15, 2021
coordination polymers, solvothermal synthesis, magnetic properties
ABSTRACT
Two new coordination polymers (Co-CPs), namely {[Co8(DCPN)4(1,2-bimb)4(μ3-OH)4]·(CH3CN)0.5(H2O)2}n (1) and {[Co2(DCPN)(1,3-bimb)(μ3-OH)]·H2O}n (2), where H3DCPN = 6-(3,5-dicarboxyl-phenyl)nicotinic acid, 1,2-bimb = 1,2-bis(imidazole-1-methyl)benzene and 1,3-bimb = 1,3-bis(imidazole-1-methyl)benzene, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis (EA), infrared (IR) analysis, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The structural analysis indicated that 1 is a 2D structure based on two different [Co4(DCPN)2(μ3-OH)2]n SBUs, and 2 is a 3D framework based on [Co4(DCPN)2(μ3-OH)2] SBUs. In addition, the magnetic measurements showed that 1 and 2 have antiferromagnetic interactions between adjacent Co(II) ions. The slight difference of magnetic properties between 1 and 2 may be attributed to their different structures formed during the assembly process.
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ArticleProbing Photocatalytic Hydrogen Evolution of Cobalt Complexes: Experimental and Theoretical MethodsWU Hai-Su, MIAO Ti-Fang*, SHI Hai-Xia, XU Yun*, FU Xian-Liang and QIAN Li
Chin. J. Struct. Chem. 2021, 40, 1696-1709 DOI: 10.14102/j.cnki.0254-5861.2011-3239
December 15, 2021
hydrogen production, cobalt complex, photocatalysis, theoretical calculation
ABSTRACT
This work reports on the synthesis and characterization of a series of Schiff-base cobalt(Ⅲ) complexes 1～4 that exhibit an obvious catalytic activity for hydrogen production in aqueous solution using fluorescein (FL) and triethanolamine (TEOA) as photosensitizer and electron donor, respectively. The complexes display the capability of splitting of water for H2 evolution. Under optimized conditions, complex 3 shows better properties for photocatalysis, 25 mg of which can release 152.3 μmol of H2 after irradiation for 3 h. The mechanism for light-driven H2 production was explored by experiments and density functional theory (DFT). Meanwhile, the reason of releasing hydrogen was explained theoretically in detail. The research results will help to understand the interaction of cobalt complexes with the photosensitizer and design new photocatalysis for the future.
- Address: Fuzhou High & New Technology Industrial Zone, Shangjie, Minhou, Fuzhou, Fujian 350108, China
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