Jian-she Zhao

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Name: 赵建社

Organization: Northwest University , China

Department: College of Chemistry & Material Science

Title: NULL(PhD)

TOPICS

Material Chemistry

Inorganic Chemistry

Metal Organic Frameworks Mesoporous Material

Chemicals
References

Preparation of mesoporous Cs-POM@MOF-199@MCM-41 under two different synthetic methods for a highly oxidesulfurization of dibenzothiophene

Co-reporter:Si-Wen Li, Jia-Rong Li, Qi-Ping Jin, Zhi Yang, Rong-Lan Zhang, Rui-Min Gao, Jian-she Zhao

Journal of Hazardous Materials 2017 Volume 337(Volume 337) pp:

Publication Date(Web):5 September 2017

DOI:10.1016/j.jhazmat.2017.04.037

•Two different methods were used to prepare the mesoporous Cs-POM@MOF-199@MCM-41.•The hybrid catalyst by substitution method shows to a best activity for the ODS process.•Stability is mainly correlated with MOF-199 and MCM-41.•The catalyst can be easily recovered and reused.Two different synthetic methods, the direct method and the substitution method, were used to synthesize the Cs-POM@MOF-199@MCM-41 (Cs-PMM), in which the modified heteropolyacid with cesium salt has been encapsulated into the pores with the mixture of MOF and MCM-41. The structural properties of the as-prepared catalysts were characterized using various analytical techniques: powder X-ray diffraction, FT-IR, SEM, TEM, XPS and BET, confirming that the Cs-POM active species retained its Keggin structure after immobilization. The substitution method of Cs-PMM exhibited more excellent catalytic performance for oxidative desulfurization of dibenzothiophene in the presence of oxygen. Under optimal conditions, the DBT conversion rate reached up to 99.6% and could be recycled 10 times without significant loss of catalytic activity, which is mainly attributed to the slow leaching of the active heteropolyacid species from the strong fixed effect of the mixture porous materials.Download high-res image (114KB)Download full-size image

Graphene/phthalocyanine composites and binuclear metal phthalocyanines with excellent electrocatalytic performance to Li/SOCl2 battery

Co-reporter:Zhijiao Liu, Qinqin Jiang, Ronglan Zhang, Ruimin Gao, Jianshe Zhao

Electrochimica Acta 2016 Volume 187() pp:81-91

Publication Date(Web):1 January 2016

DOI:10.1016/j.electacta.2015.10.145

Two new series of binuclear metal phthalocyanines and graphene/phthalocyanine composites (M2(PcTN)2C(CF3)2, M2(PcTA)2C(CF3)2, M2(PcTN)2C(CF3)2-Gr and M2(PcTA)2C(CF3)2-Gr, M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) were synthesized and developed for high efficient catalysts to Li/SOCl2 battery. All the catalysts were characterized by IR, LRS, SEM, XRD, TEM and TGA. The capacity of the battery containing these catalysts increases by approximately 4.651-83.72% than that of the battery without them. Especially capacity of Fe2(PcTA)2C(CF3)2-Gr could increase by 83.72%. In addition, the catalytic activities between M2(PcTN)2C(CF3)2 and M2(PcTA)2C(CF3)2, M2(PcTN)2C(CF3)2 and M2(PcTN)2C(CF3)2-Gr, M2(PcTA)2C(CF3)2 and M2(PcTA)2C(CF3)2-Gr, M2(PcTN)2C(CF3)2-Gr and M2(PcTA)2C(CF3)2-Gr were made a comparison. The results indicated that activities of the catalysts were related to both the phthalocyanines rings and the conjugative effect. According to the relevant CV results, reasonable catalytic mechanisms were confirmed to explain the catalytic process.

Electrocatalytic performances of multi-walled carbon nanotubes chemically modified by metal phthalocyanines in Li/SOCl2 batteries

Co-reporter:Weixing Yang, Ronglan Zhang, Kai Luo, Weiping Zhang and Jianshe Zhao

RSC Advances 2016 vol. 6(Issue 79) pp:75632-75639

Publication Date(Web):26 Jul 2016

DOI:10.1039/C6RA14456J

A series of metal 2,9,16,23-tetraaminophthalocyanines [TAPcM, M = Cu(II), Ni(II), Zn(II), Fe(II), Mn(II)] have been prepared and used to chemically modify fluorinated multi-walled carbon nanotubes (F-MWCNTs). The generated composites TAPcM/MWCNTs were characterized by IR, UV-Vis and XRD. The electrocatalytic activity of all the composites was evaluated by adding them into the electrolyte of the Li/SOCl2 battery and taking cyclic voltammograms in simulated circumstances. The results show that the composites can dramatically improve the capacity of the battery, and their electrocatalytic performance strongly depends on the metal phthalocyanine species. The order of the electrocatalytic activity of 2,9,16,23-TAPcM and 2,9,16,23-TAPcM/MWCNTs with different metal ions in the center is Mn(II) > Ni(II) > Zn(II) > Fe(II) > Cu(II). The excellent electrocatalytic performance of the modified F-MWCNTs may be due to the fine synergistic effect between the metal phthalocyanines and the MWCNTs.

Synthesis, structures, and photoluminescent properties of two uranium complexes constructed by a flexible zwitterion ligand

Co-reporter:Lingling Liang, Ronglan Zhang, Ng Seik Weng, Jianshe Zhao, Chiyang Liu

Inorganic Chemistry Communications 2016 Volume 64() pp:56-58

Publication Date(Web):February 2016

DOI:10.1016/j.inoche.2015.12.022

•Two novel uranium complexes were constructed by using a zwitterionic ligand for the first time.•Changing the anion of initial metal salts results in the structural difference of 2D and 3D networks.•The emission spectrum of the title uranium complexes were measured in the solid state.Two novel uranium complexes were constructed by using a tripodal flexible zwitterion ligand 1,1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)-tris(pyridine-4-carboxylic acid) trichlorine (H3LCl3). Reaction of uranyl acetate dihydrate and H3LCl3 in aqueous solution affords (UO2)4L2Cl4(μ3-O)2.4H2O (1), which contains tetranuclear motifs, resulting in the two dimensional structure. UO2L2.2NO3.H2O (2) obtained via the reaction of H3LCl3 and uranyl nitrate hexahydrate, which displays a three dimensional structure. The structures were detected by single crystal X-ray crystallography, elemental analysis (EA), infrared (IR) spectroscopy, and thermogravimetric analysis (TGA). Furthermore, luminescent properties were also investigated.Two novel uranium complexes were constructed by using 1,1′,1″-(2,4,6-trimethylbenzene-1,3,5-triyl)-tris(methylene)-tris(pyridine-4- carboxylic acid) trichlorine (H3LCl3) as the ligand for the first time.

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs

Co-reporter:Lingling Liang, Ronglan Zhang, Jianshe Zhao, Chiyang Liu, Ng Seik Weng

Journal of Solid State Chemistry 2016 Volume 243() pp:50-56

Publication Date(Web):November 2016

DOI:10.1016/j.jssc.2016.07.026

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) under hydrothermal condition. The combination of H3tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO2)2(H2O)4]0.5(tci)2(UO2)4(OH)4·18H2O (1), which contains two distinct UO22+ coordination environments. Four uranyl cations, linked through μ3-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals that complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (34.26.3)2(34.46.56.68.73.8). Th3(tci)2O2(OH)2(H2O)3·12H2O (2) generated by the reaction of H3tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th6O4(OH)4” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (424.64).Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite {(UO2)O2(OH)3}4n and hexanuclear {Th6O4(OH)4} motifs were found in the title actinides networks.

Synthesis and catalytic activity to Li/SOCl2 battery of asymmetric and symmetric binuclear metal phthalocyanines

Co-reporter:Q. Q. Jiang;S. W. Li;F. Yang;N. Zhao;F. X. Zhang

Russian Journal of Electrochemistry 2016 Volume 52( Issue 2) pp:136-142

Publication Date(Web):2016 February

DOI:10.1134/S102319351602004X

In our present work, the asymmetric and symmetric binuclear metal phthalocyanines (M2(PcTN)2 and M2(PcTN)2S), battery catalysts, were synthesized through microwave reaction and characterized by EA, IR and UV-vis spectroscopy. Their catalytic activity in the Li/SOCl2 battery was evaluated by adding right amount catalysts into the electrolyte. The results indicated that the capacity of the catalyzed battery increased by 6.74–67.26% and 13.41–84.36%, and the energy increased by 9.29–65.72% and 14.77–88.15% respectively, compared with the battery without phthalocyanines.

The synthesis and investigation of binuclear metal phthalocyanines as high-efficiency catalysts for Li/SOCl2 battery

Co-reporter:Fei Yang;Siwen Li;Xinyu Yang;Qinqin Jiang

Journal of Solid State Electrochemistry 2016 Volume 20( Issue 1) pp:55-65

Publication Date(Web):2016 January

DOI:10.1007/s10008-015-2975-8

Two novel series of binuclear metal phthalocyanines M2(PcHb)2 and M2(PcHb)2C (M = Co(II), Mn(II), Fe(II), Ni(II), and Cu(II)) were designed and synthesized as high-efficiency catalysts for lithium/thionyl chloride (Li/SOCl2) battery. For the sake of preparing the novel compounds, a simple and convenient method called microwave irradiation was developed. Numerous techniques including elemental analysis, Fourier transform infrared, ultraviolet–visible, and thermal gravimetric analysis were employed to characterize the final products. For the purpose of evaluating the catalytic performances of binuclear metal phthalocyanines to Li/SOCl2 battery, these compounds were operated in the electrolyte of the battery. The results revealed that the capacity of the battery had been improved approximately 15.4–46.1 %, which should be attributed to the electronic configurations of the metal ions, the phthalocyanine rings, and the synergistic effect. Among the effects of diverse metal ions on the catalytic performances of binuclear phthalocyanines, Co(II) and Ni(II) phthalocyanines were found to increase the catalytic performances to a great extent, approximately 45.1 and 46.1 %, respectively. In summary, all the evidences testified that binuclear metal phthalocyanines in this study could improve the catalyst performances dramatically when they were operated in the electrolyte of the battery.

Template method for a hybrid catalyst material POM@MOF-199 anchored on MCM-41: Highly oxidative desulfurization of DBT under molecular oxygen

Co-reporter:Si-Wen Li, Rui-Min Gao, Rong-Lan Zhang, Jian-she Zhao

Fuel 2016 Volume 184() pp:18-27

Publication Date(Web):15 November 2016

DOI:10.1016/j.fuel.2016.06.132

•A kind of novel heteropolyacid-loaded catalyst POM@MOF-199@MCM-41 was synthesized.•The structure of MOF-199 with POM encapsulated in is clear under crystal analysis.•Under O2, PMM exhibits excellent catalytic performance for deep desulfurization.•The oxidation of DBT followed pseudo-first-order kinetics.A catalyst system designed by a kind of hybrid material POM@MOF-199@MCM-41 (PMM) was found by a one pot and POM template self-construction of MOF-199 in the pore of MCM-41. This catalyst was exploited to act as a stable heteropolyacid-based one in the direct oxidative desulfurization process with a feedstock of model oil under O2 as oxidant. Based on optimal conditions, the DBT conversion reached up to 98.5% and the PMM could be recycled ten times with a slight decrease, which was compared with heteropolyacid only based on MOF-199 and MCM-41, respectively. Additionally, the structure of ordered nano-sized pores of MOF-199 with POM encapsulated in was clear under crystal analysis, which offered strong evidences for the further movement into the MCM-41.

Metal tetrabromophthalocyanines mediate the structure and electrochemical performance of lithium iron phosphate as cathode materials for lithium-ion batteries

Co-reporter:Ruiqiong Wang, Ronglan Zhang, Bei Xu, Fei Yang, Jianshe Zhao, Shichao Zhang, Junlong Wang

Journal of Electroanalytical Chemistry 2015 Volume 755() pp:47-51

Publication Date(Web):15 October 2015

DOI:10.1016/j.jelechem.2015.07.019

•LiFePO4 was modified by metal tetrabromophthalocyanine for the first time.•The composites were prepared by solvothermal followed by calcination method.•The composites were evaluated as cathodes for Li ion batteries.•All of the composites deliver highly improved performance.A novel series of cathode materials based on lithium iron phosphate (LiFePO4) for Li-ion batteries are synthesized by comprehensive utilization of solvothermal technique and high temperature calcination method. In this work, metal tetrabromophthalocyanines are utilized to control the structure of LiFePO4 and the electrochemistry of the final products is studied. The composition, structure and morphology characterizations include ICP-AES, XRD, SEM and TEM experiments. Electrochemical performance of each modified material in the Li-ion battery is evaluated by electrochemical measuring technology. The results exhibit that the as-synthesized samples can improve the initial discharge capacity of the Li-ion battery up to 150.7 mAh g− 1 at the rate of 0.1 C. In addition, the most excellent composite can enhance the rate capability of the battery dramatically compared with that of the pristine LiFePO4.

Catalytic activity of a series of subphthalocyanines in the electrolyte of Li/SOCl2 battery

Co-reporter:Rongrong Guo;Zhen Dong;Bei Xu;Chao Song

Journal of Solid State Electrochemistry 2015 Volume 19( Issue 2) pp:345-353

Publication Date(Web):2015 February

DOI:10.1007/s10008-014-2594-9

A series of subphthalocyanines with different substituents (RPhO-BSubPc(COOCH3)3) have been synthesized and used as catalysts to catalyze lithium/thionyl chloride (Li/SOCl2) battery. All the compounds are structurally characterized by IR, UV, and element analysis. After adding RPhO-BSubPc(COOCH3)3 into the battery’s electrolyte, the energy and the capacity of the battery are increased by approximately 3.27–40.6 and 10.9–53.2 % than that of the battery in the absence of them. In addition, a three-step hypothetical mechanism is figured out to explain the complex catalytic process. By comparing the images of SEM, it is found that the addition of catalysts makes the lithium chloride layer looser, which is conducive to the transfer of electrons. Moreover, the hypothetical mechanism is confirmed by the results of cyclic voltammetry.

Synthesis, characterization, and mechanism studies of bis(imino)pyridine ligands and their Cr(III) compounds

Co-reporter:S. W. Li;Y. F. Wang;X. P. Li;J. S. Zhao

Russian Journal of Coordination Chemistry 2015 Volume 41( Issue 2) pp:129-134

Publication Date(Web):2015 February

DOI:10.1134/S1070328415020050

Two new bis(imino)pyridine ligands L1, L2 (L1 = 2,6-bis[1-(4-bromophenylimino)]pyridine, L2 = 2,6-bis[1-(4-methylphenylimino)]pyridine) have been prepared. Their compounds [CrCl3L1] (I) and [Cr(Cl)(μ-Cl)(L2′)]2 (II) (L2′ = 6-bis(6-methylquinoline)pyridine) for olefin oligomerization were obtained by hydrothermal methods, during which L2′ was appeared from L2, and characterized by elemental analysis, single-crystal X-ray analysis (CIF files CCDC nos. 1025448 (I),1025447 (II)), IR spectra and melting point test. Compound I is a mononuclear compound, while compound II, bridged with the chlorine atoms, is a binuclear compound. The transformation mechanism between L2 and L2′ is also studied, and the possible reason is due to the presence of the electron-donating groups as substituents on L2. The subsequent studies on that will be carried on.

Photocatalytic performances of Ag/ALa4Ti4O15 (A = Ca, Sr and Ba) on H2O2 oxidative desulfurization

Co-reporter:Na Zhao, Siwen Li, Xin Zhang, Xinyue Huang, Jinyi Wang, Ruimin Gao, Jianshe Zhao, Junlong Wang

Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015 Volume 481() pp:125-132

Publication Date(Web):20 September 2015

DOI:10.1016/j.colsurfa.2015.04.028

•Perovskite composite oxides are outstanding catalysts in desulfurization.•The promoter Ag can improve the performance of perovskite catalysts.•Photocatalysts can reused for 5 cycles without a significant decrease in activity.•The factors that influenced desulfurization efficiency were investigated.Photocatalytic oxidative desulfurization of dibenzothiophene (DBT) with H2O2 (30%) and Ag/ALa4Ti4O15 (A = Ca, Sr and Ba) as the photocatalysts were studied. Ag cocatalyst-loaded ALa4Ti4O15 (A = Ca, Sr and Ba) were synthesized by incipient wetness. Reaction time, temperature and the amount of hydrogen peroxide were investigated as the important parameters for optimization of the reaction and a potential removal mechanism of photocatalytic oxidation was proposed. Ag (2 wt%)/CaLa4Ti4O15 and Ag (1 wt%)/BaLa4Ti4O15 were found to give remarkable catalytic activity and high selectivity for catalytic experiments. Actually, 99.0% and 98.0% of DBT were converted respectively according to the desulfurization tests. Moreover, these two catalysts were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectrum (XPS).The ODS reaction schematic shows that ultra-deep desulfurization of model fuel is proposed for the production of clean fuel. In the process of reaction, electrons and holes are generated when the perovskite composite oxides absorb photons by UV irradiation. The photogenerated holes react with hydrogen peroxide to form OH radicals, which oxidize DBT to DBTO2. It is, however, demonstrated that catalysts show superior performance for the desulfurization under the condition of the existence of hydrogen peroxide.

Synthesis, crystal structure, and magnetic properties of binuclear cobalt(II) complex with 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]-pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine

Co-reporter:X. Y. Huang;Q. Q. Jiang;J. S. Zhao

Russian Journal of Coordination Chemistry 2015 Volume 41( Issue 3) pp:202-206

Publication Date(Web):2015 March

DOI:10.1134/S1070328415030033

The synthesis and crystal structure of a new Co(II) compound with 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]-pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine (H2Ptptp) are reported. The new compound [Co2(Ptptp)Cl2(H2O)2] · H2O (I) has been determined by single-crystal X-ray diffraction (CIF file CCDC no. 1010785) and characterized by elemental analyses and infrared spectrum. The structure I consists of two independent Co2+ ions, one Ptptp2− anion, two Cl− anions, two coordinated H2O molecules and one lattice H2O molecule. The three-dimensional (3D) supramolecular architecture is formed through the hydrogen bonds among adjacent units. Moreover, magnetic susceptibility measurements indicate that the compound exhibits weak antiferromagnetic coupling interaction.

Pressure-Dependent Pseudo-Polymorphism of Polymeric {[Cu2(TBA)]·2H2O}n and Dinuclear [Cu2(TBA)(H2O)2]·2H2O Complexes Based on in Situ Tetramerization of DMBA

Co-reporter:Zhuo Li, Yu-Fang Wang, Bin Liu, Tian-Yu Zheng, Shi-Chao Zhang, and Jian-She Zhao

Crystal Growth & Design 2014 Volume 14(Issue 11) pp:5640

Publication Date(Web):September 26, 2014

DOI:10.1021/cg500935a

Two new pressure-dependent pseudo-polymorphism complexes, a 2D polymeric {[Cu2(TBA)]·2H2O}n (1) and a dinuclear [Cu2(TBA)(H2O)2]·2H2O (2), were successfully obtained and demonstrated to possess weak antiferromagnetic properties. The synthesis has been achieved through a novel one-pot reaction where four DMBA (DMBA = 1,3-dimethyl-barbitiric acid) molecules tetramerized in situ with EtOH to give (TBA)4– (H4TBA = 1,1′,2,2′-tetra-barbiturate-ethene) ligand. This unprecedented tetramerization involves one-pot formation of one new C═C bond and four new C–C bonds. It was shown that the formation of 1 strictly relied on the use of Cu(II) ion and EtOH and that reactions of oxidation, Knoevenagel condensation, and Michael addition probably induce the tetramerization.

Synthesis, characterization and crystal structures of 2D Co(II)/Zn(II)-coordination polymers containing 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole and benzenetetracarboxylate co-ligands

Co-reporter:Yu-Fang Wang, Zhuo Li, Yan-Chun Sun, Jian-She Zhao, Shi-Chao Zhang

Inorganic Chemistry Communications 2014 Volume 44() pp:25-28

Publication Date(Web):June 2014

DOI:10.1016/j.inoche.2014.02.043

•Two isomorphic Co(II)/Zn(II) complexes with the mixed-ligands are synthesized.•Domain antiferromagnetic interactions exist in Co(II) complex.•The magnetization versus field and FC/ZFC curve have been studied.•Paramagnetic behavior in Co(II) complex can be observed.•The fluorescent property of Zn(II) complex has been investigated in the solid state.Under solvothermal condition, the reaction of Co(II) or Zn(II) acetate with mixed-ligands 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (Hppt) and 1,2,4,5-benzenetetracarboxylate (H4btec) affords two isomorphic compounds [M(btec)0.5(Hppt)]n (M = Co(II) (1), Zn(II) (2)), which display the same dinodal (4,4)-connected 2D net. In addition to single-crystal X-ray crystallography, the complexes are also characterized by IR spectroscopy, PXRD, thermogravimetry, and elemental analysis. Magnetic susceptibility measurements indicate that domain antiferromagnetic interaction exists between Co(II) ions, and the paramagnetic behavior in 1 can be observed. The fluorescent property of 2 has been investigated in the solid state at room temperature.Under solvothermal condition, the reaction of Co(II) or Zn(II) acetate with mixed-ligands 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (Hppt) and 1,2,4,5-benzenetetracarboxylate (H4btec) affords two isomorphic 2D net compounds.

Synthesis, Physico-Chemical Properties and Enhanced Oil Recovery Flooding Evaluation of Novel Zwitterionic Gemini Surfactants

Co-reporter:Zhen Dong;Ying Zheng;Jianshe Zhao

Journal of Surfactants and Detergents 2014 Volume 17( Issue 6) pp:1213-1222

Publication Date(Web):2014 November

DOI:10.1007/s11743-014-1616-z

In this work, a novel series of zwitterionic gemini surfactants with different hydrophobic tails were synthesized and characterized. The physico-chemical properties of these products (such as surface tension, oil/water interfacial tension, foaming ability, and the wetting ability of paraffin-coated sandstone) were fully studied. The CMC of the synthesized surfactants ranged from 2.17 × 10−4 mol L−1 to 5.36 × 10−4 mol L−1 and corresponding surface tension (γCMC) ranged from 26.49 mN m−1 to 29.06 mN m−1, which showed excellent efficiency among the comparison surfactants. All the products can reduce the interfacial tension to a relatively low level of about 0.1–1.0 mN m−1. Additionally, results from applying different hydrocarbons suggested that the synergy will be clearer and oil/water interfacial tension will be lower if the oil components are similar to the surfactants. Contact angle and foaming measurements indicated that the surfactants exhibited good wetting and foaming abilities. The results of oil flooding experiments using an authentic sandstone microscopic model showed that C-12 and CA-12 could effectively improve the displacement efficiency by 21–29 %.

Synthesis, structure and magnetic properties of manganese(II) coordination polymer with 4,4′-[(5-carboxy-1,3-phenylene)bis(oxy)]dibenzoic acid

Co-reporter:Yanchun Sun, Yufang Wang, Zhuo Li, Jianshe Zhao, Shichao Zhang

Journal of Molecular Structure 2014 1074() pp: 416-421

Publication Date(Web):25 September 2014

DOI:10.1016/j.molstruc.2014.06.001

•One new coordination polymer based on semi-rigid polycarboxyl ligand is reported.•Crystal structure reveals the coordination polymer 1 had a three-dimensional (3D) framework.•Trinuclear Mn cluster exhibited antiferromagnetic coupling interaction with the J = −3.21 cm−1.A novel coordination polymer {[Mn2(L)4/3(H2O)3]⋅2H2O}n(1), was synthesized by the hydrothermal reaction of 4,4′-[(5-carboxy-1,3-phenylene)bis(oxy)]dibenzoic acid (H3L) with manganese(II) chloride tetrahydrate (MnCl2⋅4H2O) in an aqueous solution. The single X-ray diffraction indicated that the coordination polymer 1 had a three-dimensional (3D) framework. A trinuclear Mn unit is utilized as a building block connected via oxygen atoms of carboxylate group to form a two-dimensional layer structure. The interlayers connected by the ligands result in a 3D architecture. The coordination polymer 1 was characterized by the infrared spectroscopy, elemental analysis and powder XRD. According to magnetic susceptibility measurements the coordination polymer 1 can be characterized with the antiferromagnetic coupling interaction of J = −3.21 cm−1. Furthermore, the thermogravimetric analysis revealed good thermal stability for the coordination polymer 1.Graphical abstractA novel coordination polymer {[Mn2(L)4/3(H2O)3]⋅2H2O}n(1) was synthesized by the hydrothermal reaction. The single X-ray diffraction indicated that the coordination polymer 1 had a three-dimensional (3D) framework. A trinuclear Mn cluster is utilized as a building block connected via oxygen atoms of carboxylate group to form a two-dimensional layer structure. The interlayers connected by the ligands result in a 3D architecture. The coordination polymer 1 exhibited antiferromagnetic coupling interaction and good thermal stability.

Synthesis and structures of copper(II) and cadmium(II) compounds based on pyridazine derivative ligands

Co-reporter:S. W. Li;Y. F. Wang;J. S. Zhao

Russian Journal of Coordination Chemistry 2014 Volume 40( Issue 9) pp:653-658

Publication Date(Web):2014 September

DOI:10.1134/S1070328414080053

The two new compounds [Cu(HODA)2(H2O)2] · 3H2O (I) and [Cd(HODA)2(H2O)3] (II) (HODA = 6-oxo-1,6-dihydropyridazine-4-carboxylic acid) based on pyridazine derivation ligands have been synthesized and characterized by elemental analysis, infrared spectrum and X-ray single crystal diffraction. X-ray analysis shows that in compound I, Cu2+ ion is four-coordinated with a plane square geometry while Cu2+ ion in compound II is seven-coordinated with a distorted pentagonal bipyramid geometry. Both of the two units are all connected as 3D supramolecular structures by the intermolecular hydrogen bonds. Moreover, thermal gravimetric analysis of two compounds has been also investigated.

Synthesis and crystal structure of metal complexes based on 2,6-bis(6-methylquinolin-2-yl)pyridine ligand

Co-reporter:Y. Y. Li;X. P. Li;G. Zhang;Y. F. Wang

Russian Journal of Coordination Chemistry 2013 Volume 39( Issue 9) pp:650-654

Publication Date(Web):2013 September

DOI:10.1134/S1070328413090030

Two mononuclear five-coordinated transition metal complexes FeLCl2 (I) and MnLCl2 (II) containing tridentate 2,6-bis(6-methylquinolin-2-yl)pyridine ligand (L) have been synthesized and characterized by single-crystal X-ray crystallography. In the complexes, the metal center was tridentately chelated by ligand and further coordinated by two chlorine atoms, resulting in distorted trigonal-bipyramidal geometry for complex I and II, respectively. In addition, crystal packing in complex is stabilized by C-H⋯Cl intermolecular hydrogen bond, which link the mononuclear complex to the 1D chain.

Synthesis and physic-chemical properties of anion–nonionic surfactants under the influence of alkali/salt

Co-reporter:Zhen Dong, Xiangzeng Wang, Zhe Liu, Bei Xu, Jianshe Zhao

Colloids and Surfaces A: Physicochemical and Engineering Aspects 2013 Volume 419() pp:233-237

Publication Date(Web):20 February 2013

DOI:10.1016/j.colsurfa.2012.11.062

This paper presented a series of anion–nonionic surfactants with different hydrophobic tails and hydrophilic head-groups. Changes in physic-chemical properties of these products and their influencing factors were carefully studied. The CMC (critical micelle concentration) ranges from 1.1 × 10−2 mass% for NPS-4 to 4.8 × 10−2 mass% in the case of NPS-10. The values (γcmc) of surface tension at CMC are from 31.62 mN m−1 for NPS-4 to 44.50 mN m−1 for AES-9. Maximum surface excess concentration (Γmax) was more than 0.73 × 10−6 mol m−2and minimum area per molecule at the water/air interface (Amin) was less than 2.270 nm2 molecule−1. Results show that CMC and γcmc were efficiently improved, and the ability of reducing equilibrium interface tension (IFTeq) was weakened due to the increasing of repeat units. The study demonstrated that the detergents with the additional rigid group in the hydrophobic tail had a higher CMC than those with the alkyl chain. In addition, we figured out some IFTeq results of the surfactants solution under the influence of alkaline/salt. Ultra-low IFTeq can be obtained only when the concentration is greater than the optimal value of alkaline/salt. Dynamic interface tension (IFTdy) was analyzed and a hypothetical mechanism was used to explain the interesting phenomena IFTdy.Graphical abstractA series of anion–nonionic surfactants for EOR with different hydrophobic tails and hydrophilic head-groups was synthesized. Some physic-chemical properties of these surfactants especially the behaviors at air/water interface had been fully studied. A hypothetical mechanism was pictured above to explain the interaction of alkaline/salt and surfactant during the dynamic oil/water interface tension measurement. Firstly, when oil drop injects into solution, surfactant, alkaline and acids in crude oil migrate to the oil/water interface. Secondly, the reaction of alkaline and oil acids takes place quickly in the interface, and produces surface active species. The oil drop is deformed by the hydrophobic interaction. Interface tension instantly reduces to ultra-low. At last, we make a daring imagination that when the instantaneous interface tension is low enough about 10−4 mN m−1 the smaller drop will be obtained.Highlights► A series of anion–nonionic surfactants (alkyl polyethoxysulfonic acids) was studied. ► The values of surface tension and other physic-chemical properties were evaluated. ► The mixture of alkaline/salt and surfactants can be used as oil recovery agent. ► A model is used to explain the mechanism of dynamic interface tension.

Investigation of binuclear metal phthalocyanines as electrocatalysts for Li/SOCl2 battery

Co-reporter:Bei Xu;RongLan Zhang;JiFeng Wang;JianShe Zhao

Journal of Solid State Electrochemistry 2013 Volume 17( Issue 9) pp:2391-2400

Publication Date(Web):2013 September

DOI:10.1007/s10008-013-2103-6

Three novel series of the binuclear metal phthalocyanines M2Pc2, M2Pc2Hc, and M2Nc2 (M = Mn(II), Fe(II), Co(II), Ni(II), and Cu(II)) were synthesized and characterized. The electrocatalytic performance of the binuclear compounds to lithium–thionyl chloride battery was evaluated by operating these compounds in the electrolyte of the battery. The results indicated that the binuclear metal phthalocyanines improved the capacity of the battery by an increase of approximately 30–58 %. Of all, Cu2Pc2Hc and Fe2Nc2 displayed the highest increments of 56 and 57 %, respectively.

Synthesis and catalytic performance of MCM-41 modified with tetracarboxylphthalocyanine

Co-reporter:Ya-Ping Zhang;Ke-Chuang Xue;Wei-Ping Zhang;Chao Song;Rong-Lan Zhang

Chemical Papers 2013 Volume 67( Issue 4) pp:372-379

Publication Date(Web):2013 April

DOI:10.2478/s11696-012-0288-2

A series of tetracarboxylphthalocyanines (MPc(COOH)4, M = H, Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)) were anchored onto MCM-41 by the following procedures: functionalization of MCM-41 with (EtO)3SiCH2CH2CH2NH2 reacting with surface Si-OH, and anchoring MPc(COOH)4 onto MCM-41 with a substitution reaction between chloroformyl and amino groups. The samples were characterized by infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, N2 adsorption-desorption, and X-ray photoelectron spectroscopy. Catalytic activity of oxidation was tested using solutions of ethanethiol in petroleum ether and thiophene in octane; CoPc-CONH-MCM-41 displayed the highest conversion ratio of 90.15 % and 93.79 %, respectively.

From Two-Dimensional Double Decker Architecture to Three-Dimensional pcu Framework with One-Dimensional Tube: Syntheses, Structures, Luminescence, and Magnetic Studies

Co-reporter:Xun Feng, Jiange Wang, Bin Liu, Liya Wang, Jianshe Zhao, and Seikweng Ng

Crystal Growth & Design 2012 Volume 12(Issue 2) pp:927-938

Publication Date(Web):December 13, 2011

DOI:10.1021/cg2013717

The hydrothermal reactions of lanthanide salts with substituted imidazole-4,5-dicarboxylic acids in the presence of aliphatic carboxylates afforded a new family of lanthanide metal–organic frameworks formulated as {Y3[(Heimda)4(μ2-HCOO)·3H2O]·H2O}n (1Y), {[Gd3(Heimda)4(μ2-HCOO)·4H2O]·2H2O}n (2Gd), {[Tb3(Heimda)4(μ2-HCOO)·4H2O]·2H2O}n (3Tb) and {[Nd3(Hpimda)2(μ2-HCOO) (μ2 -C2O4)2·6H2O]·4H2O}n (4Nd), (H3eimda = 2-ethyl-1H-imidazole-4,5-dicarboxylic acid, while H3pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid). The structural diversity and photophysical and magnetic properties have been investigated. The polymer 3 triggers intense characteristic lanthanide-centered green luminescence under UV excitation, and it exhibits gradually increasing luminescence intensities when dispersed in water, ethanol, and DMSO as suspensions. After water molecules are liberated from the condensed frameworks of 4, the evacuated product (4a) exhibits nitrogen sorption properties at 77 K with a hysteresis, as well as strong characteristic emissions of the Nd(III) ion in the near-infrared (NIR) region. Polymer 2 displays very weak but significant ferromagnetic couplings between adjacent Gd(III) ions through the carboxylate bridging, whereas the depopulation of the Stark levels or possible antiferromagnetic interactions within both polymers 4 and 4a leads to a continuous decrease of χMT when the samples are cooled from 300 to 2 K.

A unique tetranuclear nickel(II) complex containing pyridine-2-carboxaldehyde derivative bearing an intramolecular acetato: Synthesis, crystal structure and magnetic property

Co-reporter:Xun Feng, Lu-Fang Ma, Li-Ya Wang, Jian-She Zhao

Inorganic Chemistry Communications 2011 Volume 14(Issue 4) pp:584-589

Publication Date(Web):April 2011

DOI:10.1016/j.inoche.2011.01.030

The novel tetranuclear nickel(II) carboxylate complex formulated as [Ni4(L)2(m2-OAc)2 (m3-OAc)2]·CH3OH·H2O, (1) (where L = 2-oxo-1,2-di(pyridin-2-yl)ethyl picolinate) has been synthesized and characterized systematically. The complex crystallizes in orthorhombic system, consisting of a tetranuclear Ni(II) distorted cubane-like core, in which four Ni(II) ions are bridged by four acetato groups. Each Ni(II) ion is further ligated with nitrogen atoms of bridging pyridine-2-carboxaldehyde derivative, forming either Ni, N, N, O- or Ni, N, O-chelate macro-rings. Magnetic susceptibility studies indicate that the weak antiferromagnetic interaction is operating between the adjacent nickel ions bridged via the carboxylate oxygen atoms within the complex.A novel tetranuclear Ni(II) carboxylate complex [Ni4(L)2(μ2-OAc)2 (μ3-OAc)2]⋅ CH3OH⋅H2O, (1) has been synthesized and characterized systematically. The complex consists of a tetranuclear Ni(II) distorted cubane-like core, in which four Ni(II) ions are bridged by two kinds of acetato groups, and each Ni(II) ion is further ligated with nitrogen atoms forming either N, N, O- or N, O-chelate rings, simultaneously. Magnetic susceptibility measurements for 1 in the temperature range of 2.0–300 K studies indicate the presence of apparent weak antiferromagnetic interaction dominates in the complex.Research Highlights► A novel tetranuclear nickel(II) carboxylate complex has been synthesized and characterized. ► The novel poly-pyridine ligand was formed unprecedentedly during the synthesis process. ► Four Ni(II) ions are bridged simultaneously by the pyridine-2-carboxaldehyde derivative and acetate ► The weak antiferromagnetic interaction was operating between adjacent nickel ions. ► The magnetic result is consistent with the bite angle of Ni- O-Ni.

A series of lanthanide–organic polymers incorporating nitrogen-heterocyclic and aliphatic carboxylate mixed-ligands: structures, luminescent and magnetic properties

Co-reporter:Xun Feng, Bin Liu, Li-Ya Wang, Jian-She Zhao, Jian Ge Wang, Ng Seik Weng and Xin-Ge Shi

Dalton Transactions 2010 vol. 39(Issue 34) pp:8038-8049

Publication Date(Web):02 Aug 2010

DOI:10.1039/C0DT00333F

Seven new lanthanide–organic coordination polymers incorporating both nitrogen heterocyclic dicarboxylate and various auxiliary ligands, {[Ln3(Hpimda)4(μ2-HCOO)·5H2O]·H2O}n} Ln = Sm (1), Ln = Eu (2), Ln = Gd (3), Ln = Dy (4), Ln = Ho (5), {[Ce2(Hpimda)2(μ4-C2O4)·8H2O]·2H2O}n (6), {[Yb2(pyda)(μ4-C2O4)2·4H2O]·3H2O}n (7) (H3pimda = 1H-2-propyl-4,5-imidazoledicarboxylic acid, H2pyda = 2,6-pyridinedicarboxylic acid) have been fabricated successfully and characterized systematically. Complexes 1–5 are isomorphous and isostructural, and are built from two-dimensional (2-D) double-decker networks based on the tetranuclear basic carboxylate as a secondary building unit (SBU). Both polymers 6 and 7 feature a (3,4)-connected 3-D framework consisting of 2-D lanthanide–organic hexagonal grids, which are further interlinked via the μ4-oxalate ligand. The results of magnetic determination show the same end-to-end bridging fashion of formate group results in different magnetic properties occurring between lanthanide centers. The luminescence emission spectra of the complexes vary depending on the lanthanide ion present.

A Series of Lanthanide−Organic Frameworks Based on 2-Propyl-1H-imidazole-4,5-dicarboxylate and Oxalate: Syntheses, Structures, Luminescence, and Magnetic Properties

Co-reporter:Xun Feng, Jianshe Zhao, Bin Liu, Liya Wang, Seikweng Ng, Gai Zhang, Jiange Wang, Xinge Shi and Yongyong Liu

Crystal Growth & Design 2010 Volume 10(Issue 3) pp:1399-1408

Publication Date(Web):February 9, 2010

DOI:10.1021/cg901391y

A family of self-assembly lanthanide−organic coordination polymers with both rigid and flexible ligands formulated as {[Ln2(Hpimda)2(μ4-C2O4)·2H2O]·4H2O}n (Ln = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), H3pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized from the reactions of H3pimda with trivalent lanthanide salts in the presence of oxalate as coligand. X-ray diffraction analysis reveals that these complexes are isomorphous and isostructural, and each forms a novel three-dimensional (3D) frameworks structure, in which the metalloligands' two-dimensional (2D) networks were constructed from the lanthanide ion, 2-propyl-imidazole-dicarboxylate as well as oxalate ligands, and the oxalate further acts as a pillar to link the [Ln(Pimda)(oxo)] 2D grids to generate the 3D open frameworks, leaving one-dimensional channels, which are occupied by water clusters displaying an intricate array. The luminescence emission spectra of the complexes vary depending on which lanthanide ion is present. In addition, compounds 3, 4, and 5 exhibited weak but significant ferromagnetic couplings within the two adjacent magnetic centers bridged through oxalato, whereas dominant antiferromagnetic interaction was observed in the erbium compound of 6, respectively.

Effect of N atoms in the backbone of metal phthalocyanine derivatives on their catalytic activity to lithium battery

Co-reporter:Zhanwei Xu, Guoxiang Zhang, Zeyuan Cao, Jianshe Zhao, Hejun Li

Journal of Molecular Catalysis A: Chemical 2010 318(1–2) pp: 101-105

Publication Date(Web):

DOI:10.1016/j.molcata.2009.11.014

Nickel(II) and Cobalt(II) Complexes with Symmetrical Four-Dentate Ligands: Crystal Structures, Characterization, and Initial DNA Binding Mechanism Research

Co-reporter:Rong-Lan Zhang;Pin Yang;Qi-Zhen Shi

Journal of Chemical Crystallography 2010 Volume 40( Issue 4) pp:357-368

Publication Date(Web):2010 April

DOI:10.1007/s10870-009-9661-6

Four new nickel(II) and cobalt(II) complexes of Schiff base ligands: [Ni(L)Cl2]·2H2O (I), [Ni(L)(H2O)2] (NO3)2 (II), [Ni(L)(H2O)2] (ClO4)2 (III), and [Co(L) (H2O)2] (NO3)2 (IV) (L = 1,3-[bis(pyridine-2-imino)]propane) have been synthesized. The four complexes have been fully characterized by elemental analysis, IR, absorption spectra, emission spectra, and single-crystal X-ray diffraction analysis. The binding of the four complexes to calf thymus DNA (CT DNA) has been investigated by absorption spectra and emission spectra. The results of the two methods indicate that the action mode of complex I with DNA is intercalative mainly, and the action mode of complexes II, III, IV with DNA cannot be concluded, it should be sustained by other experimental measurements.

A novel uranyl complex UO2(tci)(C3H5N2) · H2O: Synthesis, crystal structure and characterization

Co-reporter:Lingling Liang, Yige Cai, Ng Seik Weng, Ronglan Zhang, Jianshe Zhao, Jifeng Wang, Hongling Wu

Inorganic Chemistry Communications 2009 Volume 12(Issue 2) pp:86-88

Publication Date(Web):February 2009

DOI:10.1016/j.inoche.2008.10.027

Reaction of uranium oxynitrate hexahydrate with tris(2-carboxyethyl)isocyanurate (tciH3) in acidic aqueous solution (pH ∼4–5) yields the compound UO2(tci)(C3H5N2) · H2O. X-ray diffraction shows that the uranyl ion is in a hexagonal bipyramid structure. Uranium ion in the complex is found to be ligated with three chelating COO− groups at the equatorial plane, two oxygen atoms linking to uranium atom formed the vertical axis. The complex has the layered topology structure in the space. The thermal analysis verifies the component and the structure of the complex.As a complicated complex, UO2(tci)(C3H5N2) · H2O is prepared by uranyl ion and tciH3 which contains three nitrogen atoms, three carbonyl groups and three propionic acid groups. Each uranium atom is located in a hexagonal bipyramidal environment, surrounded by eight oxygen atoms, six of which are in the equatorial plane and are from three carboxyl groups in bidentate coordination to the UO22+ center. The remaining two oxygen atoms are terminal and occupy the two axial positions to complete the coordination sphere of the U(VI) center.

An anion-directed unprecedent three-dimensional array with erbium(III) based on the 2,6-pyridinedicarboxylate

Co-reporter:Xun Feng, Jian-She Zhao, Li-Ya Wang, Xin-Ge Shi

Inorganic Chemistry Communications 2009 Volume 12(Issue 5) pp:388-391

Publication Date(Web):May 2009

DOI:10.1016/j.inoche.2009.02.027

Reaction of 2,6-pyridine-dicarboxylic acid and ammonium oxalate with erbium salt results in the formation of a self-assembly network based upon mixed ligands of oxalate and pyridine-dicarboxylate formulated as {[Er4(pydc)2(μ4-C2O4)4]·8H2O·6H2O}n (H2pydc = 2,6-pyridine-dicarboxylic acid), in which supramolecular left-handed and right-handed helices are connected via μ4-oxalate anions, and gave the 1D coordination channels constructed via bridging oxalate and pydc ligands. The complex also displayed photo-luminescent properties in the solid state at room temperature.A novel erbium(III) coordination polymer represents the three-dimensional framework constructed via bridging oxalate and pydc mixed ligands, in which supramolecular left-handed and right-handed helices were further connected via μ4-oxolate anion, the final three-dimensional racemic framework can be considered as being constructed by helix-linked scalelike network, with one-dimensional channels filled with the coordinated water molecules as well as lattice–water molecules, and the structure is a binodal (three, four)-connected nodes net, with the Schläfli symbol (63 · 83)(83)(6 · 83).

Pyrazole-nitrogen bridged tetranuclear copper(II) cluster with an unprecedented U-like core: Synthesis, crystal structure and magnetic properties

Co-reporter:Xun Feng, Li-Ya Wang, Jian-She Zhao, Bin Liu, Jian-Ge Wang, Xin-Ge Shi

Inorganica Chimica Acta 2009 Volume 362(Issue 15) pp:5127-5132

Publication Date(Web):1 December 2009

DOI:10.1016/j.ica.2009.09.017

Reaction of 3,5-pyrazoledicarboxylic acid with copper salt under the hydrothermal condition affords a self-assembly tetranuclear copper(II) cluster based upon mixed ligands formulated as [Cu4(μ4-Pzdc)4(Im)4]·4Dma·9H2O (1) (H3Pzdc = 3,5-pyrazoledicarboxylic acid, Im = imidazole, Dma = dimethylamine), in which the four copper(II) atoms are connected into a novel Cu4N8 metallonitrogen U-like open core through eight pyrazoledicarboxylate N atoms, and the tetranuclear clusters were further interlinked through strong hydrogen bonding interactions, resulting in three-dimensional lattice supramolecular networks. The magnetic susceptibility investigation indicates that overall weak antiferro-magnetic coupling between Cu(II) cations occurs through the pyrazole-dicarboxylate bridge (J = −13.49 cm−1).Tetranuclear copper(II) cluster based upon mixed ligands has been synthesized, in which the four copper(II) atoms are connected into an unusual Cu4N8 novel metallonitrogen U-like open core through eight pyrazoledicarboxylic N atoms, and the tetranuclear motifs were connected through strong hydrogen bonding interactions to give three-dimensional lattice supramolecular frame-works.

Crystal structure and theoretical calculation of copper complexes with 4,5-diazafluoren-9-one

Co-reporter:R. L. Zhang;J. S. Zhao;X. L. Xi;P. Yang

Russian Journal of Coordination Chemistry 2009 Volume 35( Issue 1) pp:19-24

Publication Date(Web):2009 January

DOI:10.1134/S1070328409010059

Five copper complexes with 4,5-diazafluoren-9-one have been reported. Some of their structures are determined by single crystal X-ray diffraction. On the basis of experimentation, all the complexes were calculated by DFT-B3LYP/LANL2DZ in Gaussian-98w. By analyzing the experimental and calculated values, it can be concluded, on the one hand, that the experimental results are proved thoroughly by the theoretical calculated results; on the other hand, the theoretical calculated results can deduce the experimental results reasonably well.

Two novel coordination polymers [Sm2(Pzdc)3(H2O)] x · 2xH2O and [Nd2(Pzdc)3(H2O)]x · 2xH2O: Synthesis, structure, and photoluminescent properties

Co-reporter:T. L. Che;Q. C. Gao;W. P. Zhang;Z. X. Nan

Russian Journal of Coordination Chemistry 2009 Volume 35( Issue 10) pp:

Publication Date(Web):2009 October

DOI:10.1134/S1070328409100030

Coordination polymers, [Sm2(Pzdc)3(H2O)]x · 2xH2O (I) and [Nd2(Pzdc)3(H2O)]x · 2xH2O (II), were obtained by hydrothermal reactions with 2,3-pyrazinedicarboxylic acid (H2Pzdc) and the salts nitrates, and characterized by single crystal X-ray structure, thermogravimetric analysis, element analysis and infrared spectroscopy. The X-ray crystal diffraction data indicates that two complexes crystal in a monoclinic system with the space group P21/c, of the three dimensional framework. The Pzdc ligand in the complexes I and II adopts tetradentate, hexadentate, and heptadentate bridging modes. The influences of coordination modes of the Pzdc ligand on the superstructural diversity is discussed. The photoluminescent data suggest that the ligands act as efficient “antennas” sensitizing the luminescence of the Sm3+ ion. Complex I exhibits strong fluorescent emission bands in the solid state at room temperature.

A novel complex of copper(II) derived from symmetric five-dentate ligand: Synthesis, crystal structure, and characterization

Co-reporter:R. L. Zhang;J. S. Zhao;X. L. Xi;P. Yang

Russian Journal of Coordination Chemistry 2009 Volume 35( Issue 9) pp:692-697

Publication Date(Web):2009 September

DOI:10.1134/S1070328409090115

A symmetric five-dentate Schiff-base ligand N,N-bis(pyridine-2-carboxaldehyde)diethylenetriamine (L) was prepared. An unusual copper(II) complex [CuCl2 (L)] · H2O was obtained, when copper chloride reacted with ligand L. In the course of the coordination reaction, a ring closure reaction happens to ligand L. So, the formation process of the complex can be used for reference to synthesize the ring compound. The complex has been characterized fully by elemental analysis, IR, absorption spectra, emission spectra, and single-crystal X-ray diffraction analysis. Moreover, a reasonable reaction mechanism for forming the complex was presumed. The complex was synthesized by treating an ethanolic solution of the appropriate ligand with an equimolar amount of metallic salt. In the complex, the copper atom is five-coordinated, which can be best described as a distorted square-pyramidal geometry with a N3Cl2 donor set, and two parallel one-dimensional chains are formed by packing of the complex.

Synthesis, Structure and Characterization of Schiff Base Metal Complexes and Their Electrochemical Properties of Thionyl Chloride Reduction

Co-reporter:Tu-Lin CHE;Quan-Chang GAO;Gai ZHANG

Chinese Journal of Chemistry 2008 Volume 26( Issue 6) pp:1079-1084

Publication Date(Web):

DOI:10.1002/cjoc.200890191

Abstract

A symmetric tetradentate Schiff base ligand bis(3-methoxysalicylidene)-o-phenylenediamine (H₂L) was prepared. A series of transition metal complexes with this Schiff base ligand have been synthesized and structurally characterized by IR and elemental analysis. The catalysis for reduction of thionyl chloride was studied by means of constant resistance discharge. The result shows that [Mn(III)LCl(H₂O)]CH₃OH and [Co(II)HLCl(H₂O)] have a good catalytic activity for the reduction of thionyl chloride, which improves the cell voltage, the rate of discharge, and the lifetime of Li/SOCl₂batteries.

Characterization, Crystal Structure and Initial DNA Binding Mechanism Research of Multi-nuclear Homometallic Complexes of 4,5-Diazafluoren-9-one with Copper(II) and Cobalt(II)

Co-reporter:Rong-Lan ZHANG;Xiao-Li XI;Pin YANG;Qi-Zhen SHI

Chinese Journal of Chemistry 2008 Volume 26( Issue 7) pp:1225-1232

Publication Date(Web):

DOI:10.1002/cjoc.200890223

Abstract

Two new multi-nuclear homometallic complexes, [Cu₂(OAc)₄(H₂O)₂]·2dafo (1) and [(µ₂-O)₂-Co₃(dafo)₆]-(ClO₃)₂·H₂O (2) (dafo=4,5-diazafluoren-9-one), were synthesized. The two complexes have been fully characterized by elemental analysis, IR, absorption spectra, emission spectra, and single-crystal X-ray diffraction analysis. The initial DNA binding mechanisms of the two complexes have been investigated by absorption spectra, emission spectra and cyclic voltammograms. Both complexes show similar perturbations on addition of calf thymus DNA in the UV region, their luminescence intensities in aqueous buffer are all enhanced in the presence of increasing amounts of DNA, and their electrochemical behavior is both completely different in the absence and presence of DNA. The results of the three methods indicate that the spectral characters and the electrochemical behavior of the two complexes are very similar to those of the known metallointercalators. So it can be concluded that the action mode of the two complexes with DNA is mainly intercalative.

Characterization, Crystal Structure and Initial DNA Binding Interaction of Two Cu(II) Complexes with 4,5-Diazafluoren-9-one

Co-reporter:Yan-Hong SONG;Rong-Lan ZHANG;Qing-Jin SUN;Zhan-Wei XU;Quan-Chang GAO;Hua-Qiang LIU

Chinese Journal of Chemistry 2007 Volume 25(Issue 10) pp:1508-1513

Publication Date(Web):16 OCT 2007

DOI:10.1002/cjoc.200790278

Two new complexes [Cu(dafo)₂(en)](ClO₄)₂·2H₂O (en=NH₂CH₂CH₂NH₂) 1 and [Cu(dafo)₂(dap)](ClO₄)₂· 2H₂O [dap=NH₂CH₂CH(CH₃)NH₂] 2 (dafo=4,5-diazafluoren-9-one) have been synthesized and characterized by elemental analysis, IR and UV spectra. Meanwhile, the complex 1 has been characterized by single crystal X-ray diffraction analysis. The initial DNA binding interactions of the complexes 1 and 2 have been investigated by UV spectra, emission spectra and cyclic voltammogram. Concluding the results of three methods used to measure the interaction of complexes 1 and 2 with DNA, the action mode of the two complexes with DNA is intercalation, and character of ligands and steric effect may affect the interaction of the complexes with DNA.

Crystal Structure and Ethylene Oligomerization Catalytic Activity of {2-Carbethoxy-6-[1-[(2,6-diethyl-phenyl)imino]ethyl]pyridine}CoCl2

Co-reporter:Bi-Yun Sun;Quan-Chang Gao

Chinese Journal of Chemistry 2007 Volume 25(Issue 1) pp:

Publication Date(Web):8 JAN 2007

DOI:10.1002/cjoc.200790005

The unsymmetric precursor ethyl 6-acetylpyridine-2-carboxylate (4) was synthesized from 2,6-dimethylpyridine (1). On the basis of this precursor, a new mono(imino)pyridine ligand (5) and the corresponding Co(II) complex {2-carbethoxy-6-[1-[(2,6-diethylphenyl)imino]ethyl]pyridine}CoCl₂ (6) were prepared. The crystal structure of complex indicates that the 2-carbethoxy-6-iminopyridine is coordinated to the cobalt as a tridentate ligand using [N, N, O] atoms, and the coordination geometry of the central cobalt is a distorted trigonal bipyramid, with the pyridyl nitrogen atom and the two chlorine atoms forming the equatorial plane. Being applied to the ethylene oligomerization, this cobalt complex shows catalytic activity of 1.820×10⁴ g/mol-Co·h at 101325 Pa of ethylene at 15.5 °C for 1 h, when 1000 equiv. of methylaluminoxane (MAO) is employed as the cocatalyst.

Crystal structure, thermal analysis and theoretical calculation of a one-dimensional chain complex [zn(dafo)2(H2O)2](NO3)2

Co-reporter:Rong-Lan Zhang;Xin Gao;Qi-Zhen Shi;Shui-Yang He

Chinese Journal of Chemistry 2004 Volume 22(Issue 8) pp:837-840

Publication Date(Web):26 AUG 2010

DOI:10.1002/cjoc.20040220814

A novel one-dimensional chain complex [Zn(dafo)₂(H₂O)₂](NO₃)₂ was obtained when we tried synthesizing a mixed ligand supramolecular compound of Zinc(II) with dafo and o-phthalic acid. Its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic system, P-1 space group. The crystallographic data: a=0.6989(4) nm, b=0.8281(5) nm, c=1.0231(5) nm, α=94.934(5)°, β=91.366(7)°, γ=99.820(7)°, V=0.5809(5) nm³, Z= 1, F(000)=300, M_r=589.78, D_c=1.686 g/cm³, μ(Mo Kα)=1.130 mm⁻¹, R₁=0.0521, wR₂=0.1096. The analysis of the crystal structure indicates that the compound has a one-dimensional chain structure which is formed by hydrogen bonds. The constitutes of the title complex were proved by elemental analysis, IR spectra and thermal analysis. On the basis of the experimentation, the complex was calculated by DFT-B3LW/LANL2DZ in Gaussian-98w also.

Synthesis and crystal structure of a New Diamine complex CuCl4(H2tn)

Co-reporter:Gai Zhang;Rong-Lan Zhang;Xin Gao;Shao-Kang Wang;Shui-Yang He

Chinese Journal of Chemistry 2004 Volume 22(Issue 9) pp:

Publication Date(Web):26 AUG 2010

DOI:10.1002/cjoc.20040220905

In an attempt to synthesize a new pyrimidine complex of copper(II) in a solution reaction of CuBr₂ with 2,2′-bis(hexahydropyrimidine) and hydro-chloric acid, we unexpectedly obtained a bright yellow chip-like crystal of CuC₄(H₂tn) [H,tn=(H₃NCH₂CH₂CH₂NH₃)²⁺]. Its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system, space group Pnma, with cell parameters: a=0.7216(2) nm, b= 1.8308(6) nm, c=0.7553(3) nm, V=0.9953(6) nm³, Z=4, F(000)=564, M_r=281.49, D,= 1.879 g/cm³. μ(Mo Ka)=3.204 m⁻¹, R₁=0.0248, wR₂=0.0575. The analysis of the crystal structure indicates that the complex has a three-dimensional network structure, which is formed by hydrogen bonds and electrostatic interaction.

Synthesis and Crystal Structure of Two-dimensional Network Supramolecular Complex [Cu(dafo)2 (H2O)2] (ClO4)2

Co-reporter:Ai-Ping Gu;Rong-Lan Zhang;Gai Zhang;Shui-Yang He;Jian-Min Dou;Da-Qi Wang

Chinese Journal of Chemistry 2002 Volume 20(Issue 12) pp:

Publication Date(Web):26 AUG 2010

DOI:10.1002/cjoc.20020201228

In an attempt to synthesize supra-molecular complex of copper (II) with mixed ligands in a solution reaction of Cu(ClO₄)₂· 6H₂O with 4,5-diazafluorene-9-one (dafo) and o-phthalic add, the bright blue column-like crystal [Cu(dafo)₂(H₂O)₂]-(ClO₄)₂ was obtained. Its structure was determined by single-crystal X-ray diffraction study. The crystal belongs to monoclinic system, space group P2(1)/n with cell dimensions: a = 0.7547(3) nm, b = 1.2021(5) nm, c = 1.3190(5) nm, α = 90.000(5)°, β = 90.000(5)°, γ = 90.000(5)°, V = 1.2600(9) nm³, Z = 2, F(000)=670, M_r = 662.83, D_c = 1.747 g/cm³, μ (Mo Kα) = 1.154 mm⁻¹, R₁, = 0.0455, wR₂ = 0.1041. The analysis of the crystal structure indicates that the complex has a two-dimensional network structure which is formed by hydrogen bonds.

ZSM-5-Ln(Pc)2 catalyzed oxygen oxidation of thiophene

Co-reporter:Yaping Zhang, Dong Wang, Ronglan Zhang, Jianshe Zhao, Ying Zheng

Catalysis Communications (5 December 2012) Volume 29() pp:21-23

Publication Date(Web):5 December 2012

DOI:10.1016/j.catcom.2012.09.023

Direct oxidative desulfurization of thiophene with oxygen catalyzed by ZSM-5-Ln(Pc)2(NO2)6(NH2)2 (Pc = phthalocyanine) was conducted. The precursor Ln(PcTn)2 (Ln = Ce, Pr, Er, PcTn = tetra-substituted nitro phthalocyanine) was synthesized with programmed heating under nitrogen atmosphere. Then, the precursor was partially reduced by Na2S so the compound Ln(Pc)2(NO2)6(NH2)2 (Ln = Ce, Pr, Er) was obtained, which was then anchored onto ZSM-5 zeolites through the formation of secondary amine. The catalyst was characterized by XRD, SEM, XPS, and N2 adsorption–desorption. For the oxidation of thiophene with oxygen, the catalyst showed remarkable catalytic activity.Highlights► Phthalocyanine-modified ZSM-5 catalysts were prepared. ► Oxygen was chosen as the oxidant for the oxidation of thiophene. ► Reaction kinetics of the catalytic oxidation was investigated. ► Prominent reusability of the catalyst

Metal modified heteropolyacid incorporated into porous materials for a highly oxidative desulfurization of DBT under molecular oxygen

Co-reporter:Si-Wen Li, Jia-Rong Li, Yan Gao, Ling-Ling Liang, Rong-Lan Zhang, Jian-she Zhao

Fuel (1 June 2017) Volume 197() pp:

Publication Date(Web):1 June 2017

DOI:10.1016/j.fuel.2017.02.064

•Mesoporous Metal-POM@MOF-199@MCM-41 was prepared for oxidative desulfurization.•The hybrid catalyst leads to the deep DBT conversion with O2 as oxidation.•Stability is mainly correlated with MOF-199 and MCM-41.•The oxidation of DBT followed pseudo-first-order kinetics.A kind of composite catalytic materials, Metal-POM@MOF-199@MCM-41 (Metal-PMM), were obtained by confining MOF-199 encapsulating metallic Keggin POM into mesoporous MCM-41. The catalyst was designed on the stability and efficiency, which MCM-41 could act as a stable cavy for the heterogeneous metallic POM-based catalyst in the oxidative desulfurization process. The structure characteristics of the catalysts were elucidated through XRD, IR, XPS, N2 adsorption-desorption, SEM and TEM. The reaction rate could be greatly enhanced, up to 99.1%, under Co-PMM as catalyst and O2 as oxidant. After reaction, the catalyst can be simply recovered and reused more than 5 times without the change of its structure, for the strongly fixation of MOF-199 and MCM-41 to the metallic modified Keggin POM materials.

A series of lanthanide–organic polymers incorporating nitrogen-heterocyclic and aliphatic carboxylate mixed-ligands: structures, luminescent and magnetic properties

Co-reporter:Xun Feng, Bin Liu, Li-Ya Wang, Jian-She Zhao, Jian Ge Wang, Ng Seik Weng and Xin-Ge Shi

Dalton Transactions 2010 - vol. 39(Issue 34) pp:NaN8049-8049

Publication Date(Web):2010/08/02

DOI:10.1039/C0DT00333F