锡-芦丁极谱络合吸附波的研究

在pH3.9的HCOOH～HCOONa缓冲溶液中,用单扫示波极谱法可获得灵敏的Sn(Ⅳ)-芦丁(Rt)络合吸附波.在1.0×10~mol/L～6.0×10~mol/L范围内锡浓度与波高呈正比关系,检测下限可达6.0×10~(-9)mol/L.应用该法测定了罐头菠萝汁中的锡.测得电活性络合物的组成为Sn(Ⅳ):Rt=1∶1,条件稳定常数为2.7×10~4。对p_1波测得电极反应的表面电极反应速率常数(k_)_1=95s~(-1)。对P_2波测得电子转移系数α=0.60,表面电极反应速率常数(K_)_2=3.8s~(-1).     

Auxiliary Ligand Oriented Cd~(Ⅱ)-flexible Dicarboxylic Acid Coordination Frameworks:Syntheses,Structures and Properties

Two different Cd~(Ⅱ) coordination frameworks [Cd(L1)(L2)]_∞(1) and [Cd(L1)-(L3)(H_2O)]_∞(2) based on a flexible dicarboxylic acid ligand were obtained by introducing two different nitrogen heterocyclic auxiliary ligands(L1 = 3,3'-[1,3-benzenebis(carbonylimino)]bi(benzoate), L2 = 1,3-bi(4-pyridyl)propane, L3 = 4,4'-bipyridine). Complex 1 crystallizes in triclinic, space group P■ with a = 8.7415(5), b = 12.2247(7), c =16.2415(10) ?, β = 95.6790(10)°, V = 1525.11(16) ?~3, D_c = 1.553 mg·m~(-3), C_(35)H_(28)CdN_4O_6, M_r = 713.02, F(000) = 724, μ(MoKα) = 0.770 mm~(–1), Z = 2, R/wR(I 2σ(I))~a = 0.0302/0.0773. However, complex 2 crystallizes in monoclinic, space group P2_(1/n) with a = 11.4986(7), b = 23.0911(14), c = 11.9943(8) ?, β = 115.9500(10)°, V = 2863.6(3) ?~3, D_c = 1.598 mg·m~(-3), C_(32)H_(24)CdN_4O_7, M_r = 688.96, F(000) = 1392, μ(MoKα) = 0.820 mm~(–1), Z = 4, R/wR(I 2σ(I))~a = 0.0283/0.0631. The structures of two complexes were characterized. Complexes 1 and 2 have different one-dimensional(1D) chain structures. In addition, we have also made a preliminary study on the properties of the two complexes.     

μ-σ,π-苯乙烯基铁硫配合物亲核取代反应的研究——某些三苯膦或三苯胂μ-σ,π-苯乙烯基铁硫配合物的合成及结构

(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_6和PPh_3或AsPh_3在苯中回流可分别制得(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_5和PPh_3(R=Et,Bu~t,CH_2=CHCH_2)和(μ-σ,π-PhCH=CH)(μ-RS)Fe_2(CO)_5AsPh_3(R=Et,Bu~t).经X-射线衍射法测得(μ-σ,π-PhCH=CH)(μ-Bu~tS)Fe_2(CO)_5AsPh_3的单晶结构.该晶体属三斜晶系.空间群P1.晶胞参数:a=10.196(2),b=11.62(2),c=15.814(3)(?);α=102.41(1),β=91.38(2),γ=112.93(1)°;V=1673.1(?)~3,D_c=1.49g·cm~(-3),Z=2.     

乙醇-苯乙烯体系的辐解及α-羟乙基自由基反应动力学

γ射线辐照乙醇,通过苯乙烯抑制其辐解产物的研究,证明在乙醇介质中α-羟乙基自由基只进行重合反应,而无歧化反应;苯乙烯可与α-羟乙基自由基反应,其竞争反应为Sl+CH_3 CHOH→P 2CH_3CHOH→(CH_3CHOH)_2求得动力学方程为G'=G_0 k_6/2(k_7) 1/2 (G'/Dk')[Sl] G_0为纯乙醇γ射线辐照时2、3-丁二醇的产额,G_0=2.1,k_6/(k7)~(1/2)=0.53.假定k_7为扩散反应速率常数,则α-羟乙基自由基与丰乙烯加成反应的速率常数为k_6=4.0×10~4 L.mol~(-1).s~(-1).     

trans-[(en)~2(NO~2)Co(O~2CC~5H~5N)]^2^+/Fe(Ⅱ)间电子转移反应动力学及机理研究

合成了新型Co(Ⅲ)配合物trans-[(en)_2(NO_2)Co(O_2CC_5H_5N)](ClO_4)_2,并通过紫外可见光谱、红外光谱、元素分析和X射线单晶衍射分析进行了表征.同时分别以[Fe(CN)_6]~(4-)和[Fe(CN)_5(H_2O)]~(3-)作为还原剂,考察了该配合物被还原的反应动力学行为.结果表明两反应体系分别按外配位界机理和内配位界机理进行电子传递.在25℃,I=0.5mol·L~(-1),trans-[(en)_2(NO_2)Co(O_2CC_5H_5N)]~(2 )/[Fe(CN)_6]~(4-)反应体系的前驱配合物离子对形成常数Q_(ip)=29mol~(-1)·L,电子转移速率常数k_(et)=2.4×10~(-4)s~(-1),电子转移过程的活化焓△H_(et)~≠和活化熵△S_(et)~≠分别为1.2×10~2KJ·mol~(-1)和5.0×10~2J·mol~(-1)·K~(-1)在40℃,pH=8.0,I=0.1mol·L~(-1),trans-[(en)_2(NO_2)Co(O_2CC_5H_4N)]~(2 )/[Fe(CN)_5(H_2O)]~(3-)反应体系前驱双核配合物分子内电子转移速率常数为7.0×10~(-5)s~(-1).最后讨论了分子轨道对称性,两金属中心氧化还原电势差等因素对电子转移速率的影响.     

离子型碳氟与碳氢表面活性剂在胶团及吸附层中的分子间相互作用

本工作研究了二元表面活性剂溶液的热力学, 考虑了反离子对表面活性离子在表面相和胶团中的相互作用的影响, 得出计算分子相互作用参数β_m和β_σ的将遍公式(β_m和β_σ分别代表胶团和吸附层中的分子相互作用参数):β_m=ln[((cmc_1)/(cmc_1~0x_(1m)))(c″_1/c′_1)~(K_1)]/x_(2m)~2=ln[((cmc_2)/(cmc_2~0x_(2m)))(c″_2/c′_2)~(K_2)]/x_(1m)~2β_σ=ln[((c_1(π))/(c_1~0(π)x_(1σ)))(c″_1/c′_1)~(K_1)]/x_(2σ)~2=ln[((c_2(π))/(c_2~0(π)x_(2σ)))(c″_2/c′_1)~(K_2)]/x_(1σ)~2作为极限情况, 此式对于非离子型表而活性剂或有过量无机电解质时可简化为:β_m=ln[(cmc_1)/(cmc_1~0x_(1m)]/x_2m~2=ln[(cmc_2)/(cmc_2~0x_(2m)]/x_(1m)~2β_σ=ln[(c_1(π))/(c_1~0(π)x_(1σ)]/x_2σ~2=ln[(c_2(π))/(c_2~0(π)x_(2σ)]/x_(1σ)~2应用公式于各类型碳氟、碳氢表面活性剂二元混合溶液, 包括正离子-负离子、负离子-负离子、负离子-非离子混合体系。自表、界面张力-浓度关系计算各体系的β_m及β_σ。结果表明：(1)碳氟、碳氢正离子-负离子表面活性剂混合体系的β_m及β_σ有很大的负值, 表示有强烈的分子相互作用；(2)碳氟链与碳氢键间存在“互憎性”。这种“互憎性”在负离子-负离子混合体系及非离子-负离子混合体系中皆有明显表现；(3)表面压维持恒定时, 不论表面或溶液内部的表面活性剂的摩尔分数如何变化, β_σ值一般近于常数；(4)表面压越高则分子相互作用越强, 表现为β_σ绝对值变大。     

Hydrothermal Synthesis,Structural Characterization and Catalysis Property of a Zr-substituted Polyoxometalate Based on [Zr_2(μ-OH)_2(α-Si W_(11)O_(39))_2]~(10-) Building Blocks

A new Zr-substituted polyoxometalate(POM) [(CH_3)_4N]_6H_2Cs_2(H_2O)_4[Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]·27H_2O(1) was prepared by the reaction of K_(10)[A-α-SiW_9O_(34)]·25H_2O with ZrCl_4 in 0.5 mol/L NaAc-HAc(Ac = CH_3COO~-) buffer solution(pH = 4.5). 1 was characterized by elemental and thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. The title compound crystallizes in monoclinic system, space group P2_(1/m) with a = 13.1865(16), b = 20.964(3), c = 21.432(3) ?, V = 5923.9(12) ?~3, Z = 2, D_c = 3.833 mg/m~3, μ = 22.175 mm~(-1), F(000) = 6116, the final R = 0.0697 and wR = 0.1959 for 10319 observed reflections with I 2σ(I). Single-crystal X-ray structure analysis reveals that 1 exhibits a one-dimensional chain structure based on sandwiched-type POM anions [Zr_2(μ2-OH)_2(α-SiW_(11)O_(39))_2]~(10-) linked by Cs+cations. In addition, catalytic tests indicate that 1 provides a sufficient driving force for the conversion from thioethers to sulfoxides/sulfones by H_2O_2.     

间位基团激发态取代基常数的扩展及应用

合成了七个系列含间位取代基X的二苯乙烯m-XArCH=CHArY-p(简称m-XSBY-p),其中X为NO_2、I、CHCH_2、Ph、Et、NMe_2和CCH。在无水乙醇中测定它们的紫外(UV)吸收光谱,得到紫外吸收最大波长λ_(max)(nm)。对λ_(max)的波数ν_(max)(cm~(-1))进行定量相关,采用曲线拟合方法,得到上述7个间位基团的激发态取代基常数σ_(CC(m))~(ex)。将对位基团和间位基团的σ_(CC)~(ex)与Hammett常数σ进行对比,表明σx_(CC)~(ex)与σ分别表达取代基不同的电子效应。另外,合成了含上述间位基团的二芳基希夫碱(10个)和二苯乙烯(14个),用所得σ_(CC(m))~(ex)预测它们的λ_(max),并用实验测定它们的λ_(max),结果表明预测值与实验值相吻合,验证了所得σ_(CC(m))~(ex)常数的可靠性。收集了225个化合物(涉及二取代苯及二苯乙烯)的ν_(max),建立了一个统一的定量方程来表达这些化合物ν_(max)的变化规律。     

HRh[(C_6H_5)_2PCH_2CH_2P(C_6H_5)_2]_2的晶体和分子结构

HRh[(C_6H_5)_2PCH_2CH_2P(C_6H_5)_2]_2(分子量900.8)晶体属单斜晶系,空间群P21/n,晶胞参数a=21.319(2),b=20.844(2),c=10.130(3),β=91.255(2)°,V=4500.4,Z=4,D_c=1.15g·cm~(-3),F(000)=1864,μ(CuKα)=44.97cm~(-1)。共收集独立衍射点数7636个,其I>3σ(1)的衍射点数6810个。最终的R=0.045,R_w=0.050(W=1/σ~2(F)+(F)+g|F|~2)。其分子结构呈畸变的三角双锥构型。     

Hydrothermal Synthesis and Characterization of a Sandwich-type Tungstophosphate,(1,3-H2dap)8H4[Co4(H2O)2(α-B-PW9O34)2] 2·5H2O

<正>A sandwich-type tungstophosphate, (1,3-H_2dap)_8H_4[Co_4(H_2O)_2(α-B- PW_9O_(34))_2]_2·5H_2O (1,3-dap = 1,3-diaminopropane), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR and UV spectroscopy. The title compound crystallizes in triclinic, space group P1 with a = 13.691(3), b = 17.744(4), c = 20.620(5), α =113.466(5), β = 91.184(5), γ = 104.223(5)°, V = 4414.3(17)~3, C_(24)H_(96)Co_8N_(16)O_(145)P_4W_(36), M_r = 10143.09, D_c = 3.816 g/cm~3, μ(MoKα) = 24.210 mm~(-1), F(000) = 4452, Z = 1, the final R = 0.0694 and wR = 0.1519 for 9910 observed reflections (I > 2σ(I)). The compound consists of two sets of tetra-transition metal-substituted sandwich frameworks, [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) having an inversion centre. Two lacunary α-B-[PW_9O_(34)]~(9-) Keggin units are linked by a rhomb-like Co_4O_(14)(H_2O)_2 cluster, in which the Co~(2+) ions are coordinated by one water molecule. Isolatedly protonated 1,3-H2dap~(2+) units act as counter-ions to interact with the [Co_4(H_2O)_2(α-B-PW_9O_(34))_2]~(10-) heteropolyanions via hydrogen bonds, resulting in a three-dimensional framework.     

乙醇-苯乙烯体系的辐解及α-羟乙基自由基反应动力学

γ射线辐照乙醇, 通过苯乙烯抑制其辐解产物的研究, 证明在乙醇介质中α-羟乙基自由基只进行重合反应, 而无歧化反应; 苯乙烯可与α-羟乙基自由基反应, 其竞争反应为Sl+CH_3 CHOH→P 2CH_3CHOH→(CH_3CHOH)_2求得动力学方程为G'=G_0 k_6/2(k_7) 1/2 (G'/Dk')[Sl] G_0为纯乙醇γ射线辐照时2、3-丁二醇的产额, G_0=2.1, k_6/(k7)~(1/2)=0.53. 假定k_7为扩散反应速率常数, 则α-羟乙基自由基与丰乙烯加成反应的速率常数为k_6=4.0×10~4 L·mol~(-1)·s~(-1).     

Construction of a New(4,8)-Connected Coordination Polymer Based on the Zinc Cluster: Structure,Topology, and Luminescence

The title complex, [Zn_3(L)_2(H_2 O)_2]_n(1, H_3 L = 5-((3-formylphenoxy)methyl)isophthalic acid), has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Compound 1 exhibits a 3D binodal(4,8)-connected net based on trinuclear [Zn_3(COO)4] clusters with the topology symbol of(4~(16)·6~(12))(4~4·6~2)_2. It crystallizes in monoclinic system, space group P2_1/c, with a = 13.548(3), b = 13.291(3), c = 8.2750(1) ?, β = 97.08(3)°, V = 1478.7(6) ?~3, Z = 2, M_r = 858.6 g/mol, D_c = 1.928 mg/m~3, μ = 2.49 mm-1, F(000) = 864, GOOF = 1.12, the final R = 0.0457 and wR = 0.1329 for 4334 observed reflections with I 2σ(I). Additionally, the photoluminescent behaviours of 1 and H3 L have also been investigated in the solid state at room temperature.     

Effect of Anionic Ancillary Ligands on Terpyridine Based Coordination Polymers: Synthesis,Crystal Structure and Fluorescence Property

By using different anionic ancillary ligands, two new coordination polymers, [Cd(L)I_2]_n(1) and {[Cd(L)_2(1,4-bdc)]·H_2O}_n(2)(L = 2,4,6-tris(4-pyridyl)pyridine, 1,4-H_2bdc = benzene-1,4-dicarboxylic acid), have been synthesized under hydrothermal conditions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 11.625(2), b = 13.871(3), c = 13.676(3) ?, β = 108.11(3)°, V = 2096.0(7) ?~3, D_c = 2.144 g/cm~3, C_(20)H_(14)I_2N_4Cd, M_r = 676.55, F(000) = 1264, μ(MoKα) = 3.999 mm~(–1), Z = 4, Rint = 0.0308,(Δρ)_(max) = 0.354,(Δρ)_(min) = 0.289, R = 0.0332 and wR = 0.0721 for 2401 observed reflections(I 2σ(I)). However, compound 2 crystallizes in triclinic, space group P1 with a = 10.315(2), b = 14.060(3), c = 15.090(3) ?, β = 98.40(3)o, V = 1990.0(9) ?~3, D_c = 1.527 g/cm~3, C_(48)H_(34)N_8O_5Cd, M_r = 915.23, F(000) = 932, μ(MoKα)= 0.610 mm~(–1), Z = 2, Rint = 0.0776,(Δρ)_(max) = 0.869,(Δρ)_(min) = 0.843, R = 0.0815 and wR = 0.1930 for 6999 observed reflections(I 2σ(I)). Compound 1 is a 1D chain structure, which adopts inorganic anion I- as the counterion, and 2 exists a 2D(4,4) network constructed by benzene-1,4-dicarboxylic acid.     

An Organic-inorganic Hybrid Two-dimensional Bilayer Assembled from 1:2-Type [Er(α-PW_(11)O_(39))_2]~(11–)Moieties and [Cu(dap)_2]~(2+) Linkers

A new organic-inorganic hybrid phosphotungstate-based Cu~Ⅱ-Er~Ⅲ heterometallic derivative[Cu(dap)_2(H_2O)][Cu(dap)_2]_(4.5)[Er(α-PW_(11)O_(39))_2]·4H_2O(1,dap = 1,2-diaminopropane) has been hydrothermally prepared and characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.1 belongs to the triclinic space group P1 with a = 13.453(3),b =20.137(4),c = 24.565(4) A,α = 103.468(4),β = 103.829(4),γ = 98.296(4)°,V= 6148.0(19) A~3,Z =2,μ = 22.212 mm~(-1),GOOF = 1.030,R = 0.0744 and wR = 0.1700.Structural analysis indicates that1 exhibits a special two-dimensional double-layer structure constructed from l:2-type[Er(α-PW_(11)O_(39))_2]~(11-) moieties and[Cu(dap)_2]~(2+) linkers.From the topological viewpoint,1 displays a scare two-dimensional five-connected topology in which the[Er(α-PW_(11)O_(39))_2]~(11-) moieties function as the five-connected nodes.Furthermore,its thermogravimetric behavior has been studied.     

鸟嘌呤与Cu(Ⅰ)配位作用的极谱研究

在0.02mol/L NaHCO_3-0.05mol/L Na_2SO_4(pH9)介质中,对鸟嘌呤与Cu(Ⅰ)的配位作用进行了极谱研究,测定了鸟嘌呤与Cu(Ⅰ)配位的配体数(2)和该配合物的条件形成常数(β_1=1.80×10~(14),β_2=2.85×10~(18)),并对DcFord-Hume公式的适用性作了讨论.     

稀土络合催化环氧乙烷聚合

以稀土化合物-二(2-乙基己基)膦酸钕[Nd(P_(204)_3],三异丁基铝和水组成的络合催化剂,引发环氧乙烷聚合.结果表明,稀土络合催化剂是制备高分子量聚环氧乙烷的新型催化剂.聚合反应速度与环氧乙烷浓度呈一级关系,与Nd(P_(204))_3浓度呈一级关系.聚合的总活化能E_α=33.8kJ/mol,表观速率常数K_p=1.67×10~(-3)s~(-1)·mol~(-1)·1     

Two Manganese Halide Hybrids Based on 1-Butyl-2,3-dimethylimidazolium: Synthesis,Crystal Structure and Photoluminescence

Two new inorganic-organic hybrid manganese(II) halide crystals,namely[BMMIm]_2[MnCl_4](1,BMMIm=1-butyl-2,3-dimethylimidazolium) and[BMMIm]_2[MnBr_4](2),have been obtained simply by heating/stirring with nearly 100%yield.Single-crystal X-ray diffraction (SCXRD) study reveals that 1 crystallizes in triclinic space group of P1 with a=10.0176(7),b=14.9603(11),c=12.9086(8)?,a=91.060(4)°,β=110.204(5)°,g=92.361(4)°,V=1235.19(12)?~3,Z=2,D_c=1.353 g·cm~(-3),F(000)=526,μ=0.978 mm~(-1),R=0.0410 and w R=0.0690 (I2σ(I)) and M_r=503.23;2 belongs to orthorhombic space group of P2_12_12_1 with a=10.0176(7),b=14.9603(11),c=17.4450(14)?,V=2614.4(3)?~3,Z=4,D_c=1.730 g·cm~(-3),F(000)=1340,μ=6.629 mm~(-1),R=0.0440 and w R=0.0520 (I2σ(I)) and M_r=681.07.The ionic compounds 1 and 2 are composed of mononuclear tetrahedral[Mn X_4]~(2-)anion and two ionic liquid cations of[BMMIm]~+.The photoluminescence (PL)of 1 and 2 was characterized and the influence of halogen atom types on PL was investigated.     

Synthesis,Crystal Structure and Biological Evaluation of 14-O-[(2-chloroacetamide-6-aminopyrimidine-2-yl)thioacetyl] Mutilin

The title compound 14-O-[(2-chloroacetamide-6-aminopyrimidine-2-yl) thioacetyl] mutilin(4), C_(28)H_(39)ClN_4O_5S, was prepared and characterized by IR, NMR, HRMS and singlecrystal X-ray diffraction. The title compound crystallizes in orthorhombic system, space group P2_12_12_1 with a = 11.5388(8), b = 14.5282(10), c = 19.8301(14) ?, V = 3324.3(4) ?~3, Z = 4, D_c = 1.396 g/cm~3, μ(Mo Kα) = 0.462 mm~(-1), F(000) = 1464, S = 1.003, R = 0.0386 and wR = 0.1014 for 5170 independent reflections(Rint = 0.0224) with I 2σ(I)). The preliminary in vitro antibacterial bioassay against methicillin-resistant Staphylococcus aureus(MRSA-ATCC25923), Staphylococcus aureus(S. aureus), Escherichia coli(E. coli), and Staphylococcus warneri(S.warneri) were screened and the MIC values of the title compound were 0.125, 0.0625, 8 and 0.5 μg/m L, respectively.     

Synthesis,Crystal Structure and Optical and Photocatalytic Properties of a Discrete Cuprous Iodide Compound with a Transition Metal Complex Cation

With transition metal complex, a discrete cuprous iodide compound, namely, [Ni(phen)_3]_2Cu_6I_(10)(1, phen = 1,10-phenanthroline) has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1(No. 2) with a = 11.2694(2), b = 12.3699(3), c = 15.0387(3) ?, α = 102.840(2), β = 105.215(2), γ = 96.388(2)°, V = 1940.04(7) ?3, Z = 1, Dc = 2.438 g·cm~(-3), F(000) = 1324, R = 0.0256 and w R = 0.0555(I 2σ(I)). Compound 1 features a discrete anionic moiety of [Cu6I10]~(4-) charge-balanced by two metal complexes of [Ni(phen)_3]~(2+). The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant(crystal violet aqueous solution(CV), 50 m L, 1.0 × 10~(-5) M) could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.     

钠快离子导体Na1+xZr2-yTiySixP3-xO12系统研究(Ⅰ)

以Na_3PO_4、ZrP_2O_7、SiO_2、ZrO_2、TiO_2为反应原料,在1173K—1473K的高温下进行固相反应,制备了钠快离子导体Na_(1 x)Zr_(2-y)Ti_ySi_xP_(3-x)O_(12)系统中x=1、y=0—2.0的一系列合成物。研究了它们的相变关系;测定了两个单纯相—211相和202相的电导率和电导激活能。 室温时,211相的电导率σ_(RT)=1.52×10~(-4)(Ω·cm)~(-1),202相的σ_(TR)=0.53×10~(-4)(Ω·cm)~(-1);623K时,211相的电导率σ_(623)=1.21×10~(-1)(Ω·cm)~(-1),202相的σ_(623)=0.88×10~(-2)(Ω·cm)~(-1)。 在523K～673K温区里,211相的电导激活能E_a为31.87kJ/mole,202相的E_a为33.16kJ/mole。