合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀...合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm^3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10^(-2)S·cm^(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。展开更多
Eight new organo polyoxoinetalate charge transfer complexes (DH)\-6X\-2W\-\{18\}O\-\{62\}·(solv)\-n(D=Oxin(8 hydroxyquinoline), Py(Pyridine), Tol(toluene), A(aniline), DMA (N,N dimethyaniline), DEA(N,N diethylani...Eight new organo polyoxoinetalate charge transfer complexes (DH)\-6X\-2W\-\{18\}O\-\{62\}·(solv)\-n(D=Oxin(8 hydroxyquinoline), Py(Pyridine), Tol(toluene), A(aniline), DMA (N,N dimethyaniline), DEA(N,N diethylaniline), X=P, As; solv=DMF, H\-2O) was synthesized and characterized by using elemental analysis, IR, ESR. Polarographly, CV. Conductivity measurement, and X ray circle diffraction. The results showed that the crystal of (H\-2quinH)\-6P\-2W\-\{18\}O\-\{62\}·20H\-2O is Triclinic Crystal System, Space group \%P\{1-\}\%, with \%a=1.4659(5), b=2.045(8), c =2.1153(4) nm, α=90.01(3), β=87.95(2), γ=89.05(3)°, V =6.3393(35) nm\+3. This shows that under the irradiated title compound charge transfer between the organic donor and polyoxometalate anion has taken place.\;Polargraphy and cyclic Voltammetry show that the (H\-2quinH)\-6P\-2W\-\{18\}O\-\{62\}·20H\-2O undergoes three one electron reversible reduction steps in aqueous solution and four one electron quasi reversible reduction in DMF. Room temperature Conductivities of eight the title compounds ranging from 1.2×10\+\{-8\} to 3.6×10\+\{-9\} S·cm\+\{-1\} showed weak semiconducting behaviors.展开更多
The eight heteropoly complexes M4H2[PW9（NbO2）3O37]·xH2O和M4-mHm[PW11（NbO2）O39]·xH2O(M=Me4N+（TMA）,Bu4N+（TBA）,Et4N+（TEA）,He4H+（THA）were synthesized and characterized by IR,UV spectrometry,polarogra...The eight heteropoly complexes M4H2[PW9（NbO2）3O37]·xH2O和M4-mHm[PW11（NbO2）O39]·xH2O(M=Me4N+（TMA）,Bu4N+（TBA）,Et4N+（TEA）,He4H+（THA）were synthesized and characterized by IR,UV spectrometry,polarography and 183W NMR spectra.The experimantal results indicated that they were all the Keggin structure and the reduced electric potential of the complexes arised over-0.3 with entering of NbO2 groups.Experiments on oxidation of maleic acid into tartaric acid showed that the complexes containing peroxo ions exhibited higher catalytic activity than those without peroxo ions.The catalytic activity of heteropoly complexes with（NbO2）3 was higher than that of heteropoly complexes with（NbO2）.展开更多
文摘合成了未见报道的标题配合物。通过化学分析、ICP和TG曲线确定了其化学式为K_8H_3[Y(PW_(11)O_(39))_2]·25H_2O;利用IR、UV、XRD、^(183)W-NMR、循环伏安等手段对其结构进行了表征,结果表明杂多阴离子为β_2型Keggin结构。采用稀土多元渗的方法对配合物进行了气相热扩渗,经ICP和XPS测试表明:微量的稀土元素La和Ce可以渗入到配合物的体相,并与组份元素存在键合作用。扩渗后化合物的化学式为K_8H_6YLa_(0.11)Ce_(0.18)P_2W_4~ⅤW_(18)~ⅥO_(78)·15H_2O,其晶体属单斜晶系,晶胞参数:a=6.3775nm,b=3.6771nm,c=3.7727nm,β=90.192°,V=88.47326nm^3;导电性的测试结果表明:室温时,扩渗后试样的电导率提高了约10~3倍,且热稳定范围变宽,523K时的电导率为1.33×10^(-2)S·cm^(-1),有望成为实用化的导电材料;~1H MAS NMR测试结果表明其存在三种质子,其导电机理可能是质子导电。
文摘Eight new organo polyoxoinetalate charge transfer complexes (DH)\-6X\-2W\-\{18\}O\-\{62\}·(solv)\-n(D=Oxin(8 hydroxyquinoline), Py(Pyridine), Tol(toluene), A(aniline), DMA (N,N dimethyaniline), DEA(N,N diethylaniline), X=P, As; solv=DMF, H\-2O) was synthesized and characterized by using elemental analysis, IR, ESR. Polarographly, CV. Conductivity measurement, and X ray circle diffraction. The results showed that the crystal of (H\-2quinH)\-6P\-2W\-\{18\}O\-\{62\}·20H\-2O is Triclinic Crystal System, Space group \%P\{1-\}\%, with \%a=1.4659(5), b=2.045(8), c =2.1153(4) nm, α=90.01(3), β=87.95(2), γ=89.05(3)°, V =6.3393(35) nm\+3. This shows that under the irradiated title compound charge transfer between the organic donor and polyoxometalate anion has taken place.\;Polargraphy and cyclic Voltammetry show that the (H\-2quinH)\-6P\-2W\-\{18\}O\-\{62\}·20H\-2O undergoes three one electron reversible reduction steps in aqueous solution and four one electron quasi reversible reduction in DMF. Room temperature Conductivities of eight the title compounds ranging from 1.2×10\+\{-8\} to 3.6×10\+\{-9\} S·cm\+\{-1\} showed weak semiconducting behaviors.
文摘The eight heteropoly complexes M4H2[PW9（NbO2）3O37]·xH2O和M4-mHm[PW11（NbO2）O39]·xH2O(M=Me4N+（TMA）,Bu4N+（TBA）,Et4N+（TEA）,He4H+（THA）were synthesized and characterized by IR,UV spectrometry,polarography and 183W NMR spectra.The experimantal results indicated that they were all the Keggin structure and the reduced electric potential of the complexes arised over-0.3 with entering of NbO2 groups.Experiments on oxidation of maleic acid into tartaric acid showed that the complexes containing peroxo ions exhibited higher catalytic activity than those without peroxo ions.The catalytic activity of heteropoly complexes with（NbO2）3 was higher than that of heteropoly complexes with（NbO2）.
