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Synthesis,structural characterization and properties of a 3D infinitely extended structural rare earth coordination compound of K_3{[Sm(H_2O)_7]_2Na[α-SiW_(11)O_(39)Sm(H_2O)_4]_2}·14 H_2O

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Science China Chemistry 2005年第4期48卷 343-351页

作者： wang jingping zhao junwei niu jingyang Institute of Molecule and Crystal Engineering School of Chemistry and Chemical EngineeringHenan UniversityKaifeng 475001China Institute of Molecule and Crystal EngineeringSchool of Chemistry and Chemical EngineeringHenan UniversityKaifeng 475001China Institute of Molecule and Crystal EngineeringSchool of Chemistry and Chemical EngineeringHenan UniversityKaifeng 475001China

A 3D infinitely extended structural rare earth coordination compound with a formula of K3{[Sm(H2O)7]2Na[a-SiW11O39Sm(H2O)4]2}·14H2O has been synthesized by reaction of Sm2O3,HClO4,NaOH with a-K8SiW11O39·nH2O,and characterized by IR,UV spectra,ICP,TG-DTA,cyclic voltammetry,variable-temperature magnetic susceptibility and X-ray single-crystal diffrac-tion.X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lat-tice,Pi space group,with a = 1.2462(3) nm,b = 1.2652(3) nm,c = 1.8420(4) nm,α = 87.45(3)°,β = 79.91(3)°,γ = 82.57(3)°,Z = 1,R1 = 0.0778,wR2 = *** analysis reveals that Sm3+(1) coordination cation has incorporated into the vacant site of [α-SiW11O39]8? entity,forming the [α-SiW11O39Sm(H2O)4]5? *** two adjacent [a-SiW11O39Sm(H2O)4]5? subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dim-mer structural unit [α-SiW11O39Sm(H2O)4]210? of the title *** neighboring dimmer structural units [α-SiW11O39Sm(H2O)4]210? are linked to form the 1D chainlike structure by means of two Sm3+(2) and a Na+(1) coordination *** K+(1) cations connect the 1D packing chains constructing the 2D netlike structure,and adjacent netlike layers are also grafted by K+(2) cations to build the novel 3D infinitely extended *** result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554℃.The cyclic volt-ammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH = *** temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K,while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism in-teractions can be observed.

关键词： silicotungstic acid, Keggin structure, crystal structure, polyoxometalates, rare earth metal.

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Ln-substituted polytungstates as efficient hetergeneous catalysts for Knoevenagel condensation reaction

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Chinese Chemical Letters 2023年第12期34卷 361-365页

作者： Baijie Xu Ruikun zhao Zhen Jing Xinyi Ma Hui zhao Pengtao Ma jingping wang jingyang niu Henan Key Laboratory of Polyoxometalate Chemistry College of Chemistry and Chemical EngineeringHenan UniversityKaifeng 475004China

Three isomorphic polytungstates,CsgK_(18)H_(10){[Sm_(2)(H_(2)O)_(4)W_(4)O_(10)(AsW_(9)0_(33))3]_(2)(N(CH_(2)PO_(3))_(2))}:46.5H_(2)O(1),CS_(10)K_(9)H_(18){[Eu_(2)(H_(2)O)_(4)W_(4)O_(10)(AsW_(9)0_(33))_(3)]_(2)(N(CH_(2)PO_(3))_(2))}.41.5H_(2)O(2),Cs_(10)K_(9)H_(18){[Gd_(2)(H_(2)O)_(4)W_(4)O_(10)(AsW_(9)O_(33))_(3)]_(2)(N(CH_(2)PO_(3))_(2))}:46H_(2)O(_(3)),have been successfully synthesized and characterized by routine methods,and demonstrated excellent catalytic activities in Knoevenagel condensation reaction as heterogeneous ***,catalyst 1 achieved higher reaction activity than catalysts 2 and 3,where a satisfactory reaction yield(95%)and high TON value(6380)could be obtained at moderate reaction *** addition,in the scale-up experiment,with the help of catalyst 1,7.8g benzaldehyde and 5.7g ethyl cyanoacetate could transform into corresponding condensation product with a satisfactory yield(83%)and impressive TON value(13.883).

关键词： Polyoxometalates Polytungstates Lanthanide Lewis acid and base sites Knoevenagel condensation reaction

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Synthesis,structure and properties of three novel transition-metal-containing tantalum-phosphate clusters

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Chinese Chemical Letters 2022年第10期33卷 4675-4678页

作者： Xue Li Hui zhao Yuyan Li Yuanyuan Yang Mingyang Zhang Suyi Liu Pengtao Ma jingping wang jingyang niu Henan Key Laboratory of Polyxometalate Chemistry College of Chemistry and Chemical EngineeringHenan UniversityKaifeng 475004China

Peroxide ligation of aqueous metal-oxo clusters provides rich speciation and structural ***,three novel transition-metal derivatives of polyoxometalate anions,[Ni_(2)(H_(2)O)_(10){P_(4)Ta_(6)(O_(2))_(6)O_(24)}]^(6-)(1a),[Zn(H_(2)O)_(4){P_(4)Ta_(6)(O_(2))_(6)O_(24)}]^(8-)(2a)and[Cd(H_(2)O)_(4){P_(4)Ta_(6)(O_(2))_(6)O_(24)}]^(8-)(3a),have been successfully synthesized by adopting a one-pot reaction *** of these hexatantalates are built from a new-type phosphorus-incorporated *** investigated the solution behaviors,and the peak assignments of the MS spectra indicated some degree of stability of them in ***,the proton-conducting ability of compound 1a was also explored and it has shown well conductivity at high relative humidities,with conductivity achieved 1.22×10^(-3) S/cm(85℃,90%RH).

关键词： Polyoxotantalates Transition-metal Synthesize Structure Proton-conduction

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A1-D Monocopper Substituted Dawson-type Arsenotungstate (H2en)0.5[Cu(en)2]0.5{[Cu(en)2(H2O)]2[Cu(en)2](α1-As2W17CuO61)}·8H2O

A1-D Monocopper Substituted Dawson-type Arsenotungstate (H2e...

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中国化学会第四届全国多酸化学学术研讨会

作者： Yuye Li,Ziliang wang,junwei zhao~*,jingyang niu~* Institute of Molecular and Crystal Engineering,College of Chemistry and Chemical Engineering,Henan University,Kaifeng Henan 475004

Arsenotungstates(ATs) are a quite important subfamily in the polyoxometalate chemistry,which bear enormous diversity of structures and properties and attract increasing attention in the past several decades. As far as...

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An Organic-inorganic Hybrid Dimeric Arsenotungstate [enH2]4{[Cu（en）2][(A-β-H2AsW9O34)Cu（en）2]2}·8H2O Established by Two Trivacant Keggin[A-β-AsW9O34]9- fragments in the Opposite Orientation

An Organic-inorganic Hybrid Dimeric Arsenotungstate [enH2]4{...

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中国化学会第四届全国多酸化学学术研讨会

作者： Dongying Shi,junwei zhao~*,Ziliang wang,jingyang niu~* Institute of Molecular and Crystal Engineering,College of Chemistry and Chemical Engineering, Henan University,Kaifeng Henan 475004

＜正＞Polyoxometalates（POMs） are a unique class of metal-oxygen clusters of early transition metals with a tremendous structural variety and interesting properties in diverse fields such as catalysis,medicine and material ***,an important branch of POM chemistry is the design and construction of lacunary arsenotungstate species with unexpected structures and *** contrast to the abundant

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Synthesis,Characterization and Crystal Structure of an Organic-inorganic Hybrid 2-D Sheet Constructed from Dimeric Monocopper Substituted Keggin Silicotungstate Units

Synthesis,Characterization and Crystal Structure of an Organ...

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中国化学会第四届全国多酸化学学术研讨会

作者： Jie Luo,Ziliang wang,Pengtao Ma,junwei zhao~*,jingyang niu~* Institute of Molecular and Crystal Engineering,College of Chemistry and Chemical Engineering, Henan University,Kaifeng,Henan 475004

Polyoxometalates are a unique class of fascinating metal-oxygen cluster species of early transition metals with enormous structural varieties and interesting properties in catalysis,medicine,material science and ***,we have prepared a 2-D organic-inorganic hybrid sheet silicotungstate [Cu(en)(H2O)][Cu(en)][SiCuWO]·7HO(1)(en = ethylenediamine),which has been structurally

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