过渡元素三取代钨锗杂多酸盐异构体的氧化还原性质

用电化学方法研究了过渡元素三取代钨锗杂多酸盐Ｍ＇＿ｘＨ＿ｙ［ＧｅＷ＿９Ｍ＿３（Ｈ＿２Ｏ）＿３Ｏ＿（３７）］·ｎＨ＿２Ｏ（Ｍ＇＝Ｂｕ＿４Ｎ￣＋，Ｋ￣＋；Ｍ＝Ｃｒ￣３＋，Ｍｎ￣２＋，Ｃｏ￣２＋，Ｎｉ￣２＋，Ｃｕ￣２＋）的α－，β－异构体在水溶液中的氧化还原质，提出了它们的还原机理，讨论了取代的过渡元素和杂多阴离子的结构对氧化还原性质的影响，比较了两种异构体的氧化能力。     

NdSr_（1－x）M_xNiO_4（M＝Ca，Ba）的合成，结构和电学磁学性

用固相法首次合成了ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４（Ｍ＝Ｃａ：０．０≤１．０；Ｍ＝Ｂａ：０．０≤ｘ≤０．６）系列复合氧化物，并研究了其结构，红外光谱，电学性质和磁学性质。除ＮｄＣａＮｉＯ以正交晶系结晶外，其它试样的结构均属于四方晶系。ＩＲ谱显示随Ｃａ￣（２＋）离子含量的增加，ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４的Ｎｉ－Ｏ键缩短，Ｃａ￣（２＋）和Ｂａ￣（２＋）引入ＮｄＳｒＮｉＯ＿４以取代Ｓｒ￣（２＋），使试样由金属性导电转变为半导体性导电；随Ｃａ￣（２＋）含量增加，试样的室温电阻率增大。７７～３００Ｋ磁化率与温度关系曲线显示，所有试样的Ｎｉ￣（３＋）都以低自旋状态存在。     

CoMoK／γ－Al_2O_3水煤气变换催化剂的硫化及反硫化

以Ｈ＿２Ｓ和ＣＳ＿２作硫化剂，用ＴＰＳ和ＴＰＤＳ方法研究了水媒气变换催化剂ＣｏＭｏＫ／γ－Ａｌ＿２Ｏ＿３的硫化及反硫化过程。用Ｈ＿２Ｓ／Ｈ＿２硫化时，只发现Ｈ＿２Ｓ的消耗和Ｈ＿２Ｏ的生成，用ＣＳ＿２／Ｈ＿２硫化时，首先生成ＣＯ＿２，然后是ＣＨ＿４，Ｈ＿２Ｏ和Ｈ＿２Ｓ，ＴＰＧ实验表明催化剂表面上有积炭，造成催化剂的活性降低。但积炭在水煤气变换反应进行中逐渐除去。ＴＰＤＳ实验表明Ｎ＿２不起反硫化作用，Ｈ＿２和ＣＯ也没有明显反硫化作用，Ｈ＿２Ｏ对ＣｏＭｏＫ／γ－Ａｌ＿２Ｏ＿３催化剂有根强的反硫化作用。Ｏ＿２能使催化剂部分永久性失活。ＸＰＳ测试表明反硫化的催化剂中低价的Ｍｏ￣（４＋）转变成高价的Ｍｏ￣（５＋）和Ｍｏ￣（６＋），导致其活性下降。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

［M_x（FeCO_2）_yL_z］型配合物的合成、表征及CV性质研究（M＝Cu

［Ｍ＿ｘ（ＦｅＣＯ＿２）＿ｙＬ＿ｚ］型配合物可在ＴＨＦ中通Ｎ２条件下由ＦｅＣＯ＿２Ｈ和ＭＸ＿２·ｎＨ＿２Ｏ（Ｘ＝Ｃｌ￣－和Ａｃ￣－）经长时间反应制得．ＩＲ和１ＨＮＭＲ谱表明Ｃｕ（Ⅲ）、Ｃｏ（Ⅲ）属螯环配合物，Ｃｄ（Ⅱ）属四面体型配合物，Ｐｂ（Ⅱ）属线型化合物．Ｍ（Ⅱ）离子位于配合物中心．ＣＶ表明Ｍ（Ⅱ）呈多价态变化，受配体及敖合效应影响Ｆｅ（Ⅲ）Ｆｅ（Ⅱ）和Ｍ（Ⅱ）　Ｍ（０）Ｅｐ／２下降，Ｍ（Ⅱ）还原力上升．Ｍ（Ⅱ）　Ｍ（０）Ｅ＿ｐ／２随Ｍ（Ⅱ）＿（ａｑ）．性质呈现律性变化．     

电分析化学在杂多酸（盐）研究中的应用──稀土钨砷、钨镓及钨钛杂多配合物氧化还原性质的研究

应用电化学方法,系统研究ｋｅｇｇｉｎ结构稀土取代衍生物Ｌｎ（ＭＷ＿（１１）＿２（Ｍ＝Ａｓ,Ｔｉ,Ｇａ,Ｌｎ＝Ｌａ,Ｃｅ,Ｐｒ,Ｎｄ,Ｓｍ,Ｅｕ,Ｇｄ,Ｄｙ）在溶液中的氧化还原性质,得其氧化顺序,提出还原机理。     

尿素－NaBr－KBr熔体中钴及稀土－钴的电沉积

稀土－钴合金具有许多优异性能,可用于制作磁性、磁光…等功能材料。日本学者研究了在有机电解液中电沉积Ｃｏ－Ｇｄ薄膜,未见前人研究低温熔盐体系中电沉积稀土合金的报道。尿素－（７９ｍｏｌ％）－ＮａＢｒ（１９．５ｍｏｌ％）－ＫＢｒ（１．５ｍｏｌ％）的熔点为５１℃,可在１００℃左右下作为电解介质。在尿素熔体中加入ＢａＯＡｃ,能增加Ｃｏ￣（２＋）还原为Ｃｏ的阴极极化。因此选择１００℃的尿素－ＮａＢｒ－ＫＢｒ－ＮａＯＡｃ作为本底熔体,研究Ｃｏ￣（２＋）的电还原,镧、铽、镝、铥各自与钴的电解共沉积。在所研究的熔体中,Ｃｏ￣（２＋）一步不可逆还原为Ｃｏ。测定Ｃｏ￣（２＋）＋２ｅ＝Ｃｏ反应的传递系数α为０．４５,Ｃｏ￣（２＋）在熔体中的扩散系数为２．５×１０￣（－６）ｃｍ￣２·ｓ￣（－１）。稀土离子还原为稀土金属的电位很负,以致在本底熔体分解前未出现阴极波。但在含ＣＯＣｌ＿２熔体中加入ＲＥＣ＿３（ＬａＣｌ＿３、ＴｂＣｌ＿３、ＤｙＣｌ＿３、ＴｍＣｌ＿３）,使钴的析出电位向正方移动,而且阴极电流增大,因而有可能发生ＲＥ（Ｌａ、Ｔｂ、Ｄｙ、Ｔｍ）与Ｃｏ的诱导共沉积。在尿素－ＮａＢｒ－ＫＢｒ－ＮａＯＡｃ－ＣｏＣｌ＿２－ＲＥＣｌ＿３熔体     

Nd（OPr~i）_（3－n）Cl_n－AIR_3二元体系催化异成二烯聚合的研究

Ｎｄ（ＯＰｒ￣ｉ）＿（３－ｎ）Ｃｌ＿ｎ－ＡＩＲ＿３二元体系催化异成二烯聚合的研究蔡小平，龚志，王佛松，朱行浩（中国科学院长春应用化学研究所，长春１３００２２）（吉林化学工业公司研究院，吉林１３２０２１）关键词聚异成二烯，二元钕催化剂，定向聚合，稀土催...     

非活化苯环的缩合反应

让过氧化来甲酰和五氯化钼与氯苯反应，生成一个新的双核钼配合物［（Ｃ＿６Ｈ＿４Ｃｌ）＿２Ｃ（ｐｈ）］＿２［Ｍｏ＿２（μ－Ｃｌ）＿３Ｃｌ＿４Ｏ＿２］［Ｍｏ＿２（μ－Ｃｌ）＿２Ｃｌ＿４Ｏ＿２（μ－ＯＣＯＰｈ）］。用Ｘ－射线单晶衍射的方法测定了它的晶体结构。同时还研究了该化合物的谱学性质，并用ＡＳＥ—ＭＯ方法计算了它的电子结构。     

K_（17）［Ln（As_2W_（17）O_（61）_2］·xH_2O的合成和

合成了稀土钨砷系列杂多化合物Ｋ＿（１７）［Ｌｎ（Ａｓ＿２Ｗ＿（１７）Ｏ＿（６１）＿２］·ｘＨ＿２Ｏ并经红外、极谱和￣（１８３）ＷＮＭＲ对其进行了表征，在［Ｌｎ（Ａｓ＿２Ｗ＿（１７）Ｏ＿（６１）＿２］￣１７－中Ｗ原子有９种不同配位环境，Ｌｎ与８个氧原子配位。     

四苯基卟啉锌[ZnTPP(H_2O)]的晶体结构及性质研究

用X射线衍射法确定了四苯基卟啉锌（Ⅱ）水合物ZnC44H28N4（H2O）的晶体结构。晶体属于单斜晶系，C2空间群，a=18903（4），b=9．672（2），c=13．379（3）A，β=134．92（3）°，V=1732（1）A3，Z=2，Dx=1．335g／cm3，Mr=696．13，μ（MoKa）＝0．764mm－1,F（000）=720。最终偏离因子R=0．055，Rw=0．050（1076、个I≥3σ（I）衍射点）。配合物分子中Zn（Ⅱ）离子落入卟啉空腔内与4个吡咯氮原子共平面，在垂直该平面上与H对H2O分子呈轴向配位，其分子结构呈四方锥型。用电子吸收光谱和1HNMR波港以及循环伏安法对其性质进行表征，并对其轴向配位反应的热力学性质进行研究。     

Synthesis,characterization, and properties of semifluorinated organo‐soluble new aromatic polyamides

A series of organo‐soluble new polyamides were synthesized by the direct polycondensation of different semifluorinated aromatic diamines, namely 4,4‐bis[3'‐trifluoromethyl‐4'(4“‐amino benzoxy)benzyl]biphenyl; 4,4”‐bis(aminophenoxy)‐3'3“‐trifluoromethyl terphenyl; 1,3‐bis[3'‐trifluoromethyl‐4'(4”‐amino benzoxy)benzyl]benzene; 2,6‐bis(3'‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine; and 2,5‐bis(3'‐trifluoromethyl‐p‐aminobiphenyl ether)thiophene with 5‐t‐butyl‐isophthalic acid. The polymers were fully characterized by elemental analysis and IR, NMR spectroscopies. The synthesized polyamides were soluble in several organic solvents such as 1‐methyl‐2‐pyrrolidone, N,N‐dimethylformamide, N,N‐dimethylacetamide, tetrahydrofuran, and dimethyl sulfoxide at room temperature. They showed inherent viscosities of 0.42–0.63 dl/g. The polyamides exhibited weight‐average molecular weights of up to 233,000, which depended on the exact repeating unit structure. The polyamides synthesized from 4,4‐bis[3'‐trifluoromethyl‐4'(4”‐amino benzoxy)benzyl]biphenyl and 5‐t‐butyl isophthalic acid exhibited highest glass‐transition temperatures 261°C (evaluated by differential scanning calorimetry) in nitrogen. These polyamides showed good thermal stability up to 475°C for a 10% weight loss in air. The polyamides films were clear and flexible in nature with tensile strengths of up to 88 MPa, modulus of elasticity of up to 1.81 GPa, and elongations at break of up to 25%, which depended on the exact repeating unit structure. X‐ray diffraction measurements indicated that these polyamides were amorphous in nature. Copyright © 2010 John Wiley & Sons, Ltd.     

Salen型化合物的合成、表征及性质

设计合成了两种新型Salen配体H2L1(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二甲氧基-1,2-苯二胺)、H2L2(N,N?-3-二甲氧基-邻羟苯亚甲基-4,5-二硝基-1,2-苯二胺)及相应的镍、铜、锌金属配合物ML1、ML2(M=Ni,Cu,Zn),并分别采用核磁共振(1HNMR)波谱、紫外-可见(UV-Vis)吸收光谱、红外(IR)光谱、质谱(MS)和元素分析进行了表征.探究了配体及其配合物的荧光性质.研究发现,与H2L1相比,配体H2L2由于引入强的吸电子基团―NO2,其荧光强度减弱.相对于配体,锌离子的配位则导致其配合物的荧光强度增强,而镍和铜离子的嵌入则使得配合物ML1、ML2(M=Ni,Cu)荧光猝灭.对电化学性质的研究表明,CuL1的氧化还原过程为准可逆的单电子过程;与H2L2相比,配体H2L1由于引入强的给电子基团―OCH3,其溶液的导电性降低.     

Ancillary ligand-controlled assembly of three coordination polymers: synthesis,characterization, luminescent,and catalytic properties

Abstract

By changing the ancillary ligands, three new zinc-based coordination polymers (CPs), {[Zn(4,4′-bpy)(H₂O)₄]·(TDC)·(H₂O)}_n (1), [Zn(2,2′-dmbpy)(TDC)]_n (2), and [Zn₂(3,3′-dmbpy)(TDC)₂]_n (3) (H₂TDC =2,5-thiophenedicarboxylic acid, 4,4′-bpy =4,4′-bipyridine, 2,2′-dmbpy =2,2′-dimethyl-4,4′-bipyridine, 3,3′-dmbpy =3,3′-dimethyl-4,4′-bipyridine) have been synthesized under the same reaction conditions (H₂O, pH =7–8, and 140°C) and were structurally characterized. 1 is a linear chain structure and further connected into a 3-D structure through hydrogen bonds. 2 shows a 2-D (4,4) network when the dinuclear [Zn₂(COO)₄N₂] building unit is regarded as a six-connected node. 3 has a twofold-interpenetrating 3-D zinc-organic framework pcu topology. Furthermore, 1–3 show strong photoluminescence at room temperature in the solid state, and the catalytic activities of 1–3 for degradation of methyl orange in a Fenton-like process have been investigated. The results suggest that the ancillary ligands influence the final resulting CPs.     

Synthesis, Mesogenic and Spectroscopic Properties of 2,5-Disubstituted Thiophene Derivatives

Two series of 2,5-disubstituted thiophene derivatives （series 1： 2,5-bis（p-alkoxyphenylethynyl）thiophene and series 2： 2,5-bis[p-（p-alkoxyphenylethynyl）（phenylethynyl）]thiophene） were synthesized and characterized by ^1H NMR, ^13C NMR, HRMS and elemental analysis. The relationship between the structure and the mesogenic and spectroscopic properties has been discussed. The results show that compounds 1a-1f all exhibited an enantiotropic nematic mesophase, which was confirmed by the polarized optical microscopy （POM）, differential scanning calorimeter （DSC） and variable temperature powder X-ray diffraction （PXRD）. In contrast, the extended conjugated analogues 2a-2b had no liquid crystal properties. As for the spectroscopic properties, incorporating more phenylethynyl units results in red-shifted absorption and emission spectra, greatly enhanced quantum efficiency.     

Synthesis,Structure, Magnetic and Optical Properties of Ternary Thio‐germanates: Ln4(GeS4)3 (Ln = Ce,Nd)

Single crystals of two ternary thio‐germanates containing rare‐earth metals, Ln₄(GeS₄)₃ (Ln = Ce ( I ), Nd ( II )), have been isolated from the reaction of anhydrous rare‐earth trichloride (LnCl₃) and ternary sodium thio‐germanate (Na₂GeS₃) in evacuated quartz ampoules. We have determined the crystal structure of the compounds, which are isostructural to La₄(GeS₄)₃ and crystallize in trigonal system in the space group R3c with the cell dimensions: I , a = b = 19.375(3) Å, c = 8.028(2) Å, Z = 6; II , a = b = 19.250(3) Å, c = 7.949(2) Å, Z = 6. The structure is built with the complex network of two independent tricapped trigonal prisms of CeS₉, in which Ge atoms occupy tetrahedral holes of sulfur atoms. The bulk synthesis of the two compounds has also been achieved by the stoichiometric combination of the elements. The magnetic and optical properties of the compounds have been investigated. The magnetic moments of 2.32 and 3.49 μ_B for I and II , respectively, are in good agreement with the theoretical magnetic moments of Ce and Nd in the +3 oxidation state. The optical band gap of I is found to be located around 2.3 eV, while the optical band gap of II lies around 2.62 eV. In addition, Raman spectroscopic characterizations have also been performed for I , II , and La₄(GeS₄)₃.     

Syntheses,structures, and properties of copper and cadmium complexes with quinoline-based benzimidazole

A new tridentate ligand 2-((quinolin-8-yloxy)methyl)benzimidazole (L) and three coordination compounds, [CuLCl₂] (1), [CuL(H₂O)(SO₄)?· 2H₂O] _n (2), and {[Cd₂L₂Cl₄][CdLCl₂(H₂O)]₂}?·?H₂O (3), have been synthesized and characterized. Single crystal structure analyses reveal extensive intermolecular hydrogen bonding, resulting in generation of 1-D–3-D supramolecular networks. Compounds 1 and 2 constitute the first examples of Cu complexes containing both 8-hydroxyquinoline and benzimidazole, while 3 represents the first Cd complex bearing this ligand. Complexes 1–3 show similar quasi-reversible electrochemical behaviors. Complex 2 exhibits a predominantly ferromagnetic interaction between copper centers, and 3 has good fluorescence and can be used as an optical material.     

羟基卟啉化合物的电化学、顺磁共振及时间分辨光电压性质

通过循环伏安法、电子顺磁共振谱和时间分辨电压光谱研究了羟基取代基数目和位置的不同对羟基苯基卟啉化合物的电化学、电子顺磁共振和时间分辨光电压性质的影响. 研究结果表明, 所有氧化还原反应都是在卟啉环上进行的. 卟啉周边取代基数目的增加使得卟啉共轭体系平均电子云密度增大, 导致体系易氧化而难以还原. 对称性增强可能使卟啉化合物的半波电位值向正方向移动, 羟基取代基的给电子效应对于卟啉化合物电化学性质的影响起主导作用. 常态下卟啉分子没有EPR信号, 在光的激发下, 卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子, 这种激发三重态分子在分子轨道上具有两个未成对电子, 这两个电子相距很近, 彼此之间发生很强的相互作用而产生电子, 它的g值随卟啉共轭体系平均电子云密度增大而变大. 时间分辨光电压是由分子中的自由光声载流子的存在而产生的, 光电压的衰减与分子结构密切相关, 它们的电荷分离速度基本上随卟啉周边羟基取代基数目的增加而减慢.     

L-精氨酸铜配合物的磁性、铁电与热重研究

为了合成和研究具有磁性和铁电双重性能的配合物,本文选用L-精氨酸(L-Arg)配体与硝酸铜制备了一个配合物,其组成为[Cu(L-Arg)2]2+(NO3-)2·3H2O(1),单晶X射线衍射分析表明,该配合物的晶体结构属于单斜晶系手性空间群C2。磁性和铁电性能测试表明该配合物具有弱的铁磁行为和铁电双重性能。热分析显示该配合物在77-150℃失去自由水,从243℃开始分解。     

One polyoxometalate-based hybrid 3-D network: synthesis,structure, photo- and electro-catalytic properties

A new polyoxometalate-based inorganic–organic hybrid material, H₅Ag(Bbi)_1.5(Bbi)₂[P₂W₁₈O₆₂] (1) (Bbi?=?1,1-(1,4-butanediyl)-bis(imidazole)), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and thermogravimetric analysis. In 1, adjacent [P₂W₁₈O₆₂]^6? (short for P₂W₁₈) anions are connected through Ag by equatorially positioned terminal oxygen atoms to generate a 1-D chain. Adjacent chains were further connected through Ag and two-coordinated Bbi ligands into a (6,?3)-layer, which are extended to 3-D supermolecule nets through H bonds. The photo- and electro-catalytic properties of 1 have been studied.