(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷与镧系硝酸盐、硫氰酸盐配合物的合成表征和CD谱

合成了共15个未见文献报道的三价镧系离子与手性氮杂冠醚(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷(以下以L(+)表示)的配合物Ln(NO₃)₃·L(+)·H₂O(Ln=La、Ce、Pr、Nd); Ln(SCN)₃·L(+)·H₂O(Ln=La、Pr、Nd、Sm、Eu、Gd-Er、Yb)。对所合成配合物进行了元素分析、电导、红外、可见吸收光谱、比旋光度和圆二色谱(CD谱)的测试，并对配合物的有关物理化学性质进行了讨论。     

一种铽配合物用于水溶液中二甲硝咪唑和四环素的检测

选用(1,1'':3'',1″-三联苯)-3,3″,4'',5,5″,6''-六羧酸(H₆L)为配体,在溶剂热条件下,与Tb³⁺离子反应得到配合物[Tb (L)_0.5(H₂O)₂]·7H₂O (1)。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、热重分析对该配合物的结构和组成进行了表征,同时,对其荧光性质进行了研究。结果表明:该配合物属于正交晶系,Cmca空间群,a=2.661 61(7) nm,b=1.421 03(4) nm,c=2.109 88(6) nm。拓扑计算表明配合物1是一个新颖的(6,6)-连接的三维网络结构,符号为(4⁸.6⁶.8)(4⁹.6⁶)。该配合物具有强的荧光发射,可以快速检测水溶液中的二甲硝咪唑和四环素且灵敏度高、检出限低、可回收性好。通过实验和密度泛函理论相结合,揭示了荧光猝灭机理。     

基于2-硫代巴比妥酸构筑零维原子簇{[Cu6(H2tba)6]·2DMF·xSolvent}、二维层状{[Sc(H2tba)3(DMF)]·2DMF}n和三维网状{[Fe(H2tba)2(H2O)2]·2DMF}n

分别以Cu (ClO₄)₂·6H₂O、Sc (ClO₄)₃·6H₂O和Fe (ClO₄)₃·9H₂O为金属盐,2-硫代巴比妥酸(H₃tba)为配体,通过扩散反应得到了3种不同结构的配合物{[Cu₆(H₂tba)₆]·2DMF·xSolvent}(1)、{[Sc (H₂tba)₃(DMF)]·2DMF}_n(2)和[Fe (H₂tba)₂(H₂O)₂]_n(3),并用红外光谱、元素分析、热重分析和粉末X射线衍射对配合物进行了表征。单晶X射线衍射结构分析表明配合物1是一个具有三方反棱柱构型的六核铜原子簇合物,配合物2是一个具有二维层状结构的化合物,配合物3是一个具有三维网状结构的配位聚合物。配合物1在390 nm光照激发下在735 nm处有强的荧光发射峰。     

基于4-甲基邻苯二甲酸和4,4′-联吡啶混合配体的镉的配合物的合成、结构及荧光性质

通过Cd(OAc)₂·2H₂O与4-甲基邻苯二甲酸(H₂L)及4,4′-联吡啶(bpy)在水热条件下反应得到一个新型的配位聚合物{[Cd(L)(bpy)(H₂O)₂·2H₂O]}_n(1), 并用元素分析, 红外, 热重, 粉末衍射及单晶X-射线分析法对配合物的结构进行了表征。配合物首先展示二维层状的网络结构, 再进一步通过丰富的氢键堆积成三维超分子结构, 另外, 本文还研究了该配合物的荧光性质。     

Phen-铜(II)-氨基酸配合物的合成、表征及其SOD活性

合成了3个新的SOD模拟配合物：[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O (1)、[Cu(Phen)(L-Ala)(H₂O)]Cl·4H₂O (2)、[Cu(Phen)(L-Thr)(H₂O)]Cl·2H₂O (3) [Phen(1，10-邻菲咯啉)、L-Gln(谷氨酰胺)、L-Ala(丙氨酸)、L-Thr(苏氨酸)]。用元素分析、摩尔电导、红外光谱、紫外-可见光谱对配合物进行了表征。用X-射线衍射对配合物[Cu(Phen)(L-Gln)(H₂O)]Cl·2H₂O的晶体结构进行了测定。用氯化硝基四氮唑蓝(NBT)光还原法对这3个配合物催化歧化超氧阴离子自由基(O₂^{- ·})的能力进行了测定。结果表明：这些配合物具有较高的SOD活性， 催化速率常数K_Q分别为1.58 × 10⁷ mol^-1·L·s^-1、5.65 × 10⁷ mol^-1·L·s^-1、0.83 × 10⁷ mol^-1·L·s^-1。     

两种三齿多吡啶铜(Ⅱ)配合物的合成、表征及其与DNA的作用

本文合成了2个三齿多吡啶铜(Ⅱ)配合物[Cu(phpi)Cl₂]·H₂O和[Cu(tpy)Cl₂]·2H₂O(phpi=2-(苯并咪唑基-2)-1，10-邻菲咯啉，tpy=2，2:6′，2″-三联吡啶)，并通过元素分析、摩尔电导率、红外光谱、紫外光谱对其进行了表征。应用电子吸收光谱、荧光光谱和粘度法研究了配合物与DNA的相互作用。在抗坏血酸存在下，利用琼脂糖凝胶电泳方法研究了配合物对pBR322 DNA的切割作用并对其作用机理作了初步探讨。     

吡啶-2,5-二羧酸钐(Ⅲ)、镝(Ⅲ)配合物的合成、结构及性质

以Sm(NO₃)₃·6H₂O、Dy(NO₃)₃·6H₂O、吡啶-2,5-二羧酸(H₂pydc)为原料, 用水热合成法合成了2个新的稀土金属配合物[Ln(pydc)₂(H₂O)₅]·4H₂O(Ln=Sm (1), Dy (2)), 单晶结构经X单晶衍射仪分析确定, 两种配合物的晶系均为单斜晶系, C2/c空间群。对晶体的性质进行元素分析、热重、红外光谱, 荧光等分析。结果表明, 配合物1和2在常温下表现出稀土离子相应的特征荧光发射。另外, 本文对两种配合物进行了热稳定性及动力学分析。     

基于3，4'，5-联苯三羧酸构筑的钕配合物的合成、结构、荧光、光催化及磁性质

采用NdCl₃·6H₂O和3,4'',5-联苯三羧酸（H₃bpt）为原料在DMF/H₂O混合溶剂热条件下合成得到一个三维钕配合物{[Nd （bpt）（DMF）（H₂O）]·2H₂O}_n（1）,并通过红外光谱、元素分析、单晶及粉末X射线衍射表征了配合物1的结构。单晶衍射结果表明,配合物1具有（5,5）-连接的三维结构,拓扑符号为（4⁴·6³·8³）（4⁸ 6²）。此外,对配合物1的热稳定性、荧光性质、光催化降解染料及磁性质进行了详细研究。     

杯[4]芳烃修饰的钌(Ⅱ)配合物的合成与性质

合成了一种新颖的杯[4]芳烃修饰的钌（Ⅱ）配合物[Ru₂（bpy）₄（H₂L）]（ClO₄）₄（1）（bpy=2,2''-联吡啶,H₂L=11,23-双（2-咪唑[4,5-f]-1,10-菲啰啉）-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃）,并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液（1：100,V/V）中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的"off-on-off"型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F^-和OAc^-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。     

杯[4]芳烃修饰的钌(II)配合物的合成与性质

合成了一种新颖的杯[4]芳烃修饰的钌（Ⅱ）配合物[Ru₂（bpy）₄（H₂L）]（ClO₄）₄（1）（bpy=2,2''-联吡啶,H₂L=11,23-双（2-咪唑[4,5-f]-1,10-菲啰啉）-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃）,并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液（1∶100,V/V）中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的“off-on-off”型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F^-和OAc^-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。     

Chemical ionization mass spectrometry—XIX: n-hexane and n-octane as reactants

The suitability of n-hexane and n-octane as reactant gases in chemical ionization mass spectrometry has been investigated. The mass spectra of these substances have been investigated as a function of pressure up to 2·4 Torr for n-hexane and 1·7 Torr for n-octane. The major ion present in n-hexane at 0·8 Torr is [C₆H₁₃]⁺ (m/e 85) with a relative intensity of 0·65. In n-octane at 0·8 Torr the major ions are [C₈H₁₇]⁺ (m/e 113), [C₆H₁₃]⁺ (m/e 85) and [C₅H₁₁]⁺ (m/e 71). The relative intensities of these ions are 0·38, 0·12 and 0·19, respectively. These alkyl ions in both n-hexane and n-octane are thought to have tertiary structures. Rate constants for the rates of reaction of the primary ions in the two compounds have been determined. The n-hexane chemical ionization spectra of 26 compounds were determined. The spectra of polar compounds are dominated by proton transfer, whereas those of nonpolar compounds exhibit proton transfer and in addition often surprisingly large amounts of electron transfer. The n-octane chemical ionization spectra of 15 compounds were determined and the spectra in general are quite similar to those obtained with n-hexane. n-Hexane and n-octane can be used as reagents in analytical chemical ionization mass spectrometry, but except in certain specialized uses they would probably have no advantage over i-butane.     

Investigation of desolvation process in lanthanide dinicotinates

The desolvation process in lanthanide pyridine-3,5-dicarboxylates of the formulae [Tb₂pdc₃(dmf)₂]·dmf (1), [Ho₂pdc₃(dmf)₂]·dmf (2), [Erdc₃(dmf)₂]·dmf (3), and [Yb₂pdc₃(dmf)₂]·dmf (4) where pdc-C₅H₃N(COO)₂²⁻, dmf-N,N′-dimethylformamide) has been investigated by means of the TG–DSC, TG–FTIR, IR and XRD methods. Heating of the complexes in the range 30–260 °C lead to evolution of weakly bonded dmf molecules included in the channels as well those directly bonded with lanthanide atoms. The kinetic analysis revealed a multistep desolvation pattern.     

Thermal decomposition of inclusion compounds on the base of the metal–organic framework [Zn4(dmf)(ur)2(ndc)4]

Inclusion compounds based on metal–organic frameworks (MOFs) have promising practical applications in gas storage, the separation, and fine purification of substances, and also in catalysis. These MOFs are crystalline compounds consisting of metal ions coordinated by bridging organic ligands with the formation of porous structures. We study the kinetic stability of two inclusion compounds on the base of the new framework: [Zn₄(dmf)(ur)₂(ndc)₄]·6C₆H₆ and [Zn₄(dmf)(ur)₂(ndc)₄]·5C₆H₅CH₃ (ndc^2? = 2,6-naphtalenedicarboxylate, ur = hexamethylentetramin, dmf = N,N′-dimethylformamide). The inclusion compound with benzene is more stable than the compound with toluene. The reduced stability of the toluene compound may be connected with the toluene molecule’s shape: the C₆H₅CH₃ molecule is more bulky and asymmetric than the C₆H₆ molecule; the MOF matrix structure must be greatly distorted to include the toluene molecules and the compound stability decreases.     

Synthesis,crystal structure,and properties of a tetrairon cluster based on 2-methyl-8-hydroxyquinoline

The synthesis, structure, and magnetic properties of a tetrairon(III) complex [Fe₄(μ₂-O)₂Cl₄(L)₄]·0.5H₂O (1, L = 2-methyl-8-hydroxyquinoline), which was prepared under solvothermal conditions and characterized by IR spectra, elemental analysis, TG, and single-crystal X-ray crystal diffraction, are presented. Each Fe center adopts a distorted trigonal bipyramid geometry and is coordinated with three oxygen atoms, one nitrogen atom, and one chlorine atom. Each 2-methyl-8-hydroxyquinoline is coordinated to two Fe^III ions with μ₂-η²:η¹ coordination mode. The magnetic properties of the complex are dominated by antiferromagnetic exchange interactions.     

Spectroscopic,electrochemical and X-ray crystallographic properties of a novel palladium(II) complex of thioamide deprotonated di-2-pyridyl ketone thiosemicarbazone (dpktsc-H)−

The reaction between di-2-pyridyl ketone thiosemicarbazone (dpktsc) and PdCl₂(CH₃CN)₂, generated in situ from the reaction between PdCl₂ and CH₃CN, gave the unprecedented [Pd₂Cl₃(κ⁵-N_py,N_im,S,N_py,N_am-dpktsc-H)]·2CH₃CN (1) complex (py = pyridine, im = imine and am = amide). The identity of 1 was confirmed via its elemental analysis and spectroscopic properties. Infrared and ¹H-NMR spectra confirmed the coordination of (dpktsc-H)^? to the palladium ions. The electronic absorption spectra measured in dmso and dmf and density functional theory (DFT) calculations revealed metal-to-ligand charge-transfer (MLCT), d–d and intra-ligand charge-transfer (ILCT) electronic transitions. X-ray structural analysis on a crystal of [Pd₂Cl₃(κ⁵-N_py,N_im,S,N_py,N_am-dpktsc-H)]·H₂O (2) grown from dmf solution of 1 confirmed its formulation and showed the solid-state structure contains a web of molecules locked via a network of non-covalent interactions. Electrochemical measurements on 1 in dmf revealed metal- and ligand-based redox processes. In contrast to the electrochemical decomposition of uncoordinated dpktsc, coordinated (dpktsc-H)^? in 1 does not undergo electrochemical decomposition. Electrochemical titrations of 1 with p-toluenesulfonic acid monohydrate (p-TSOH) revealed electro-catalytic proton reduction. Over-potential (η) of 180 mV for the H₂ evolution was observed and is comparable to several molecular electro-catalysts for proton reduction. Controlled-potential electrolysis confirmed the electro-catalytic proton reduction by the Pd-complex. Electrochemical reactions of CO₂ in the presence of 1 exhibited a proton dependence, and metal- and ligand-based electrochemical reaction.     

Structural Diversity of Copper(II) Coordination Polymers Based on Tosylated Isophthalic Ligands

Two tosylated isophthalic ligands, namely, 5‐tosyloxy‐isophthalic acid (H₂toip) and 5‐tosylamino‐isophthalic acid (H₂taip) were synthesized. Self‐assembly of Cu^II ions with H₂toip and H₂taip ligands under different reaction conditions (temperature, solvents, and auxiliary ligands) gave rise to three coordination polymers formulated as [Cu(toip)(py)₂]_n ( 1 ), [Cu₆(toip)₆(H₂O)₆]_n · 8n(H₂O) ( 2 ), and [Cu₆(taip)₆(py)₄(dmf)₂]_n · n[(dmf)₆(MeOH)₂(H₂O)₂] ( 3 ) (py = pyridine, dmf = dimethylformamide). Compound 1 is a one‐dimensional (1D) coordination polymeric chain. Compounds 2 and 3 are two‐dimensional (2D) coordination networks featuring very similar Kagomé lattices based on the interconnection of paddle‐wheel [Cu₂(COO)₄] secondary building units (SBUs) and toip^2–/taip^2– ligands. However, the arrangement of adjacent Kagomé lattices in 2 and 3 are distinct, making them crystallize in different space groups and thereby have different crystal structures.     

希土离子-pmap-吡啶氧化物混配配合物的制备及性质研究

合成了Ce(pmap)_4·2H_2O(pmap=1苯基-3 甲基-4-乙酰基-吡唑酮-5);Ln(pmap)_3·2H_2O·xC_2H_5OH(Ln=La-Nd,x=1;Ln=Sm,Eu-Lu,x=0)以及Ln(pmap)_3·L·H_2O(Ln=La-Lu;L=pyno, 3picno,4picno)等固体配合物,并对它们进行了热谱、电导、红外和可见——紫外光谱等的测试工作。观察到镧系收缩;吡啶氧化物上甲基的取代位置对混配配合物热稳定性的影响;Pr~(3 ),Nd~(3 ),Ho~(3 ),Er~(3 )离子配合物在可见区有超灵敏跃迁现象;从XPS光谱知不同希土离子结合能的对数值与原子序数间有直线关系。     

Kinetics and Mechanism of Radical‐Chain Oxidation of 1,2‐Substituted Ethylene and 1,4‐Substituted Butadiene‐1,3

A combination of microvolumetry, the rotating sector method, ESR, ¹H NMR, and IR allowed to establish a detailed mechanism of liquid‐phase oxidation of vinyl compounds X₁CH=CHX₂ and X₁CH=CH–CH=CHX₂ (X₁ and X₂—a polar substitute: С₆Н₅–, CO–, СOO–) initiated by azobisisobutyronitrile. A distinctive feature of the mechanism is the fact that the oxidation chain is carried out by a low‐molecular hydroperoxide radical joining the π‐bond. For nine compounds in the temperature range of 303–353 K, relative chain propagation and termination rate constants were measured (k ₂•k ₃^−0.5). Absolute values of k ₂ were obtained for diphenylethylene (110 L·mol⁻¹·s⁻¹), ethyl ether of trans‐phenyl‐pentadiene acid (13 L·mol⁻¹·s⁻¹), and methyl ether of trans‐phenyl‐pentadiene acid (14.2 L·mol⁻¹·s⁻¹) at T = 323 K. For the same conditions, 10⁻⁸k ₃ were calculated for diphenylethylene (0.87 L·mol⁻¹·s⁻¹) and methyl ether of trans‐phenyl‐pentadiene acid (1.21 L·mol⁻¹·s⁻¹). A cyclic mechanism of the oxidation chain termination on introduced antioxidants (stable nitroxyl radicals of the piperidine series ( > NO^●) and the transition metal compounds (Meⁿ )) was established. The inhibition factor (f ) showing how many reaction chains are terminated by the one particle of the antioxidant is equal to 10². The cyclic chain termination is caused by the following reactions: HO₂^● + > NO^● → NOH + O₂, HO₂● + NOH → >NO^● + H₂O₂ (for >NO^●) and HO₂^● + Meⁿ → Me^{n +1} + HO₂^●−, HO₂^● + Me^{n +1} → Meⁿ + H⁺ + O₂ (for Meⁿ ).     

Cobalt(II) Complexes with Dicyanamide — from Binuclear Entities to Chains

One binuclear complex [Co(bpm*)₂(dca)]₂(ClO₄)₂ ( 1 ) and two 1D chain Co^II complexes, {[Co(bpm)₂(dca)](ClO₄)}_n ( 2 ) and [Co(dmf)₂(dca)₂]_n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R₁ = 0.0672, wR₂ = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each Co^II ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R₁ = 0.0609, wR₂ = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of Co^II ions bridged by one dca ligand. Each Co^II ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C₂, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R₁ = 0.0260, wR₂ = 0.0760. 3 has a one‐dimensional linear chain of Co^II ions bridged by two dca ligands, in which each Co^II ion is coordinated with two dmf molecules.     

Thermal and spectroscopic properties of light lanthanides (III) and sodium complexes of 2,5-pyridinedicarboxylic acid

Pyridine-2,5-dicarboxylic acid, known as isocinchomeric acid is one of six isomers containing two carboxylic groups. Light lanthanide (III) complexes with pyridine-2,5-dicarboxylic acid with general formula Ln₂L₃·nH₂O, where n = 8, 9, were obtained. Their thermal and spectroscopic properties were studied. Sodium salt was obtained as Na₂L·H₂O. Hydrated complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) are stable to 313–333 K, whereas Na₂L·H₂O is stable to about 333 K. Dehydration process for all compounds runs in one stage, next they decompose into appropriate lanthanide oxalates, oxocarbonates carbonates and finally to metal oxides. Bands of νCOOH vibrations at 1736 and 1728 cm⁻¹ disappear on complex spectra and ν_as and ν_s of COO⁻ groups appear thus indicating that complexation process took place.