柔性1，5-二（2-乙基咪唑）戊烷配体构筑的两个d10金属配合物的合成、结构及性质

摘要：利用过渡金属镉（锌）盐与1,5-二（2-乙基咪唑）戊烷（BEIP）、5-羟基间苯二甲酸（5-OHH₂IP）在水热条件下合成了配合物[Cd（BEIP）（Cl）₂]_n（1）和[Zn（BEIP）（5-OHIP）]_n（2）,并对其进行了元素分析、IR及X射线衍射法表征。晶体结构研究表明：配合物1属于正交晶系,Pca2₁空间群。配合物2属于单斜晶系,P2₁/n空间群,β=100.542（4）°。配合物1是由配体1,5-二（2-乙基咪唑）戊烷连接镉离子形成一维链状结构。而配合物2是由配体间苯二甲酸连接锌离子形成一维链状结构,该一维链通过1,5-二（2-乙基咪唑）戊烷连接成二维网络结构,进而通过氢键连接成三维超分子结构。此外,配合物1和2具有较高的稳定性和较好的荧光性能,配合物2对甲基橙染料有一定的降解作用。     

柔性1,5-二(2-甲基咪唑)戊烷配体构筑的两种锌配合物的合成、结构及性质

利用过渡金属锌盐与1,5-二（2-甲基咪唑）戊烷（BMIP）、5-羟基（或5-溴）间苯二甲酸（5-OHH₂IP或5-BrH₂IP）在水热条件下合成了配合物[Zn（5-OHIP）（BMIP）]_n（1）和[Zn（5-BrIP）（BMIP）]_n（2）（BMIP=1,5-二（2-甲基咪唑）戊烷,5-OHIP=5-羟基间苯二甲酸根,5-BrIP=5-溴间苯二甲酸根）,对其进行了红外、元素分析表征并用单晶X射线衍射确定了其结构。晶体结构研究表明：配合物1属于单斜晶系,P2₁/n空间群,β角为101.363（10）°。配合物1是由配体5-羟基间苯二甲酸连接锌离子形成一维链状结构,然后由1,5-二（2-甲基咪唑）戊烷将其连接成二维网络结构。配合物2是由配体5-溴间苯二甲酸和1,5-二（2-甲基咪唑）戊烷连接锌离子形成二维层状结构,由另一方向的1,5-二（2-甲基咪唑）戊烷连接成三维层柱状结构,最终形成三重贯穿网络结构。此外,研究了配合物1和2的荧光和光降解亚甲基蓝性能,结果表明配合物1和2对亚甲基蓝染料均有较好的降解作用。     

柔性1,5-二(2-乙基咪唑)戊烷配体构筑的两个d10金属配合物的合成、结构及性质（英文）

利用过渡金属镉(锌)盐与1,5-二(2-乙基咪唑)戊烷(BEIP)、5-羟基间苯二甲酸(5-OHH_2IP)在水热条件下合成了配合物[Cd(BEIP)(Cl)_2]_n(1)和[Zn(BEIP)(5-OHIP)]_n(2),并对其进行了元素分析、IR及X射线衍射法表征。晶体结构研究表明:配合物1属于正交晶系,Pca2_1空间群。配合物2属于单斜晶系,P21/n空间群,β=100.542(4)°。配合物1是由配体1,5-二(2-乙基咪唑)戊烷连接镉离子形成一维链状结构。而配合物2是由配体间苯二甲酸连接锌离子形成一维链状结构,该一维链通过1,5-二(2-乙基咪唑)戊烷连接成二维网络结构,进而通过氢键连接成三维超分子结构。此外,配合物1和2具有较高的稳定性和较好的荧光性能,配合物2对甲基橙染料有一定的降解作用。     

刚性1,4-二(4-甲基咪唑)苯配体构筑的两个d10配位聚合物的合成、结构及荧光性质

利用过渡金属镉（锌）盐与1,4-二（4-甲基咪唑）苯、间苯二甲酸分别采用分层和水热法合成了化合物{[Cd（BMIB）（H₂O）₂]（NO₃）₂}_n（1）和{[Zn₂（BMIB）_1.5（OH）（IP）_1.5]·H₂O}_n（2）（BMIB=1,4-二（4-甲基咪唑）苯,IP²-=间苯二甲酸根）,并对其进行了元素分析、IR及X射线衍射法表征。晶体结构研究表明：配合物1属于三斜晶系,P1空间群。晶胞参数：a=0.382 08（3）nm,b=0.904 72（7）nm,c=1.378 29（10）nm,α=98.581（4）°,β=97.020（3）°,γ=94.398（3）°。配合物2属于单斜晶系,C2/c空间群。晶胞参数：a=3.764 07（9）nm,b=1.017 18（5）nm,c=2.015 31（11）nm,β=120.860（2）°。配合物1是由配体BMIB连接镉离子形成一维链状结构,由氢键连接成二维层结构。而配合物2是由配体IP^2-连接锌离子形成一维梯状结构,该一维梯通过羟基和BMIB连接成三维网络结构。此外,配合物1和2具有较好的荧光性能。     

刚性1,4-二(4-甲基咪唑)苯配体构筑的两个d10配位聚合物的合成、结构及荧光性质

利用过渡金属镉（锌）盐与1,4-二（4-甲基咪唑）苯、间苯二甲酸分别采用分层和水热法合成了化合物{[Cd（BMIB）（H₂O）₂]（NO₃）₂}_n（1）和{[Zn₂（BMIB）_1.5（OH）（IP）_1.5]·H₂O}_n（2）（BMIB=1,4-二（4-甲基咪唑）苯,IP^2-=间苯二甲酸根）,并对其进行了元素分析、IR及X射线衍射法表征。晶体结构研究表明：配合物1属于三斜晶系,P1空间群。晶胞参数：a=0.382 08（3）nm,b=0.904 72（7）nm,c=1.378 29（10）nm,α=98.581（4）°,β=97.020（3）°,γ=94.398（3）°。配合物2属于单斜晶系,C2/c空间群。晶胞参数：a=3.764 07（9）nm,b=1.017 18（5）nm,c=2.015 31（11）nm,β=120.860（2）°。配合物1是由配体BMIB连接镉离子形成一维链状结构,由氢键连接成二维层结构。而配合物2是由配体IP2-连接锌离子形成一维梯状结构,该一维梯通过羟基和BMIB连接成三维网络结构。此外,配合物1和2具有较好的荧光性能。     

间苯二甲酸和二咪唑基苯构建锌化合物的合成, 晶体结构和荧光性质

由水热法合成了锌化合物[Zn₂(dib)(1,3-BDC)₂(H₂O)](1),1,3-H₂BDC=间苯二甲酸,dib=1,4-二咪唑基苯),并进行了元素分析、IR、TG及X-射线衍射法表征。晶体结构表明:配合物1属于单斜晶系,P2₁/n空间群。配合物1是由羧酸配体间苯二甲酸阴离子连接成一维双链,然后由1,4-二咪唑基苯连接成层状,此二维结构被氢键拓展成三维超分子结构。     

三个基于1,5-二(2-乙基苯并咪唑基)-戊烷柔性配体的镉配合物

通过设计柔性配体1,5-二（2-乙基苯并咪唑基）戊烷（bep）,在二羧酸辅助配体的调控下成功制备了3个配位聚合物[Cd（bep）（sba）]_n（1）,[Cd（bep）（bda）]_n（2）,and{[Cd₂（bep）（ada）₂]·H₂O}_n（3）（H₂sba=4,4’-磺酰基二苯甲酸,H₂bda=4,4’-联苯二甲酸,H₂ada=1,3-金刚烷二乙酸）。配合物均呈现二维层状结构。配合物1由交替的Cd（Ⅱ）/bep/sba^2-螺旋链构成。配合物2由Cd/bda^2-单元构成二维结构,bep作为单齿配体与Cd（Ⅱ）配位。配合物3的二维层通过Cd/ada^2-/H₂O氢键螺旋链拓展成三维超分子。此外,对配合物1~3的粉末X射线衍射、热稳定性以及荧光性质进行了研究。     

基于3,5-二(3-吡啶)-4-氨基-1,2,4-三唑配体的Co(Ⅱ)和Cu(Ⅱ)配合物的合成与晶体结构

利用3,5-二（3-吡啶）-4-氨基-1,2,4-三唑（L）配体与Co（Ⅱ）/Cu（Ⅱ）盐室温下反应得到了一维的配位聚合物{[CoL（H₂O）₄]SO₄·H₂O}_n（1）和单核配合物[Cu（hfac）₂L₂]（2,hfac=hexafluoroacetylacetonate）。通过红外、元素分析及X射线单晶衍射等检测手段对所合成的配合物进行了表征。结构研究表明,配合物1中,配体L呈顺式构型,采取双齿配位方式桥联Co（Ⅱ）离子形成一维正弦链状结构,一维链通过多种氢键相互作用连接进一步形成三维网状结构;溶剂水分子和硫酸根阴离子通过氢键连接在框架上。配合物2中,配体L则采取单齿配位方式,与Cu（Ⅱ）离子形成离散型的单核结构,通过多重氢键作用进而连接成三维网状结构。     

三个基于1，5-二(2-乙基苯并咪唑基)-戊烷柔性配体的镉配合物

通过设计柔性配体1,5-二（2-乙基苯并咪唑基）戊烷（bep）,在二羧酸辅助配体的调控下成功制备了3个配位聚合物[Cd（bep）（sba）]_n（1）,[Cd（bep）（bda）]_n（2）,and{[Cd₂（bep）（ada）₂]·H₂O}_n（3）（H₂sba=4,4’-磺酰基二苯甲酸,H₂bda=4,4’-联苯二甲酸,H₂ada=1,3-金刚烷二乙酸）。配合物均呈现二维层状结构。配合物1由交替的Cd（Ⅱ）/bep/sba^2-螺旋链构成。配合物2由Cd/bda^2-单元构成二维结构,bep作为单齿配体与Cd（Ⅱ）配位。配合物3的二维层通过Cd/ada^2-/H₂O氢键螺旋链拓展成三维超分子。此外,对配合物1~3的粉末X射线衍射、热稳定性以及荧光性质进行了研究。     

三个Zn(Ⅱ)/Co(Ⅱ)配位聚合物的合成、结构与光带能隙

通过使用两性离子羧酸配体4-羧基-1-（4-羧基苄基）吡啶盐（L1）和含氮辅助配体1,4-二（咪唑-1-甲基）苯（L2）或1,3-二（咪唑-1-甲基）苯（L3）分别与金属锌盐和金属钴盐反应,合成了配合物[Zn（L1）（L2）_0.5Cl]_n（1）、[Co（L1）（L2）_0.5Cl]_n（2）和{[Zn（L1）（L3）]ClO₄·1.7H²O}_n（3）。配合物1和2同构,具有（6,3）拓扑的二维层状结构。该二维层进一步通过倾斜穿插形成三维结构。配合物3具有一维铰链结构。相邻的一维链进一步通过π-π作用扩展为二维层状结构。值得注意的是,配合物1~3均可视为由一维[M（L1）]_n链和桥联的双咪唑基配体L2或L3构成。配合物1和2是由一维的螺旋链和Z形的桥联L2配体构成,而配合物3是由一维的之字形链和C形的桥联L3配体构成。研究结果表明不同的含氮辅助配体和阴离子对配合物的最终结构有重要的影响。光带能隙研究表明,配合物1~3的能带间隙分别为2.96、1.72和3.16 eV,这表明配合物具有潜在的宽隙半导体的性质。     

Synthetic Cu0.507(5)Pb8.73(9)Sb8.15(8)I1.6S20.0(2) nanowires

Nanowires of an iodine containing Pb-Sb-sulfosalt have been synthesized by chemical vapor transport. Their structure was studied using high-resolution transmission electron microscopy and X-ray powder diffraction. The lattice parameters show values equal to a=4.9801(4) nm, b=0.41132(8) nm (with two-fold superstructure), c=2.1989(1) nm and β=99.918(6)°. These parameters and the results of a multislice simulation are in good agreement with the mineral pillaite, Cu_0.10Pb_9.16Sb_9.84S_22.94Cl_1.06O_0.5 (space group C2/m, a=4.949(1) nm, b=0.41259(8) nm, c=2.1828(4) nm, and β=99.62(3)°). Microprobe and EDX analyses yielded a chemical composition of Cu_0.507(5)Pb_8.73(9)Sb_8.15(8)I_1.6S_20.0(2) which is close to natural pillaite but contains no oxygen and iodine instead of chlorine. The structure of the investigated material is based on chains of M-S polyhedra (M=Pb or Sb) typical for the architecture of sulfosalts implying iodine atoms in trigonal prismatic coordination with Pb atoms from the M-S polyhedra of neighboring chains. The [010] superstructure of the specimen was found to be unstable under electron beam irradiation with a rapid decrease of the b lattice parameter from 0.8 to 0.4 nm within 5 min.     

The magnesium-rich intermetallics Ir3.30(1)Mg17.96(4)In0.74(4) and Ir3Mg17.1(1)In1.9(1)

Phase analytical investigations in the system magnesium-iridium-indium revealed the magnesium-rich intermetallics Ir_3.30(1)Mg_17.96(4)In_0.74(4) and Ir₃Mg_17.1(1)In_1.9(1). The samples were prepared from the elements via induction melting in glassy carbon crucibles in a water-cooled sample chamber and subsequent annealing. Both intermetallics were investigated by X-ray powder and single-crystal diffraction: C2/c, Z=4, a=979.1(1), b=2197.4(2), , β=105.79(1)°, wR₂=0.0434, 3076 F² values, 108 variables for Ir_3.30(1)Mg_17.96(4)In_0.74(4), and a=983.39(8), b=2211.4(2), , β=105.757(6)°, wR₂=0.0487, 3893 F² values, and 115 variables for Ir₃Mg_17.1(1)In_1.9(1). Both compounds show solid solutions. In Ir_3.30(1)Mg_17.96(4)In_0.74(4), the indium site shows an occupancy by 69.9(4)% In+30.1(4)% Ir, and one magnesium site has a small mixed occupancy with indium, while nine atomic sites in Ir₃Mg_17.1(1)In_1.9(1) show Mg/In mixing with indium occupancies between 1.2(3)% and 14.8(3)%. The relatively complex crystal structure is of a new type. It can be explained by a packing of coordination number 10 and 12 polyhedra around the iridium atoms. The crystal chemical peculiarities and chemical bonding in both intermetallics is briefly discussed.     

Chemiluminescence from poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) block copolymers

A detailed analysis of the chemiluminescence emission (CL) from poly(styrene-b-ethylene-co-butylene-b-styrene), SEBS, was carried out. A phenol-phosphite stabilization system based on Irgafos 168 and Irganox 1330, was studied. The kinetic analysis of the CL profile under nitrogen shows a first-order reaction for the decay of chemiluminescence. The activation energy shows different values as a function of temperature, showing that different reactions are involved in the thermal degradation of the SEBS. The CL decay rate correlates well with the amount of the phosphite, Irgafos 168, and confirms the activity of this stabilizer as radical chain-breaking antioxidant in these copolymers.The isothermal analysis of CL under oxygen allows evaluation of the oxidation state, as well as the efficiency of the antioxidants. Good correlations are found between the CL parameters and concentration of Irgafos 168. Several factors suggest that oxidation begins in the interfacial region. Spectral analysis of the chemiluminescence shows the presence of different types of hydroperoxides.Finally, the characterization of the SEBS copolymers by differential scanning calorimetry reveals an order-disorder transition, assigned to aggregates that behave as paracrystalline regions.     

Novel (E)- and (Z)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles from (E)- and (Z)-3-styrylchromones: the unexpected case of (E)-3(5)-(2-hydroxyphenyl)-4-(4-nitrostyryl)pyrazoles

An efficient synthetic method for the preparation of (E)- and (Z)-3(5)-(2-hydroxyphenyl)-4-styrylpyrazoles has been developed. The reaction of (E)- and (Z)-3-styrylchromones with hydrazine hydrate afforded the corresponding (E)- and (Z)-4-styrylpyrazoles, respectively, saved 4′-nitro-derivatives where both (E)- and (Z)-4′-nitro-3-styrylchromones afforded (E)-3(5)-(2-hydroxyphenyl)-4-(4-nitrostyryl)pyrazoles. The reaction mechanism for these transformations was discussed and the stereochemistry of all products was assigned by NMR experiments.     

C(膜)/Si(SiO2)(纳米微粒)/C(膜) 的光致发光性质研究

用直流辉光溅射法结合真空镀膜法制备出了一种"多层三明治结构"的光致发光材料-C(膜)/Si(SiO2)(纳米微粒)/C(膜)夹层膜,然后分别在400、650和750℃退火1 h.在波长为250 nm的紫外光激发下,刚制备出来未经退火处理的样品具有一个在398nm(3.12 eV)处的紫光宽带PL1峰.在650℃退火后,又出现了一个在360nm(3.44eV)附近的PL2峰.PL1和PL2峰形状和峰位与退火温度和激发波长无关,但强度却与退火温度和激发波长密切相关.结合形态结构分析可知,紫光PL1峰可用量子限制-发光中心(QC-LCs)模型进行解释:即光激发发生在8iO2微粒内部,而光发射源于SiO2与Si界面上的缺陷中心.紫外荧光PL2峰则源自SiC内部的电子-空穴复合发光.     

Sublimation enthalpies of the complexes W(CO)6-x(NCCH3)x (x=1,2,3) and Mo(CO)6-x(NCCH3x(x=1,3)

Vapour pressure measurements have been carried out on the complexes W(CO)_it6-x (NCCH₃x(x=1,2,3) and Mo(CO)_it6-x(NCCH₃x(x=1,3) employing the Knudsen effusion technique. The following enthalpies of sublimation, ΔH²⁹⁸_sub(kJ mole^?1), have been determined from vapour pressure data: W(CO)₅(NCCH₃)=98.1±2.0; W(CO) ₄ (NCCH₃)₂=131.0±6.0; W(CO)₃(NCCH₃₃=103.4±6.0; Mo(CO)₅(NCCH₃)=105.8± 5.6; and Mo(CO)₃(NCCH₃)₃=111.3±3.0.     

Asymmetric dihydroxylation route to (R)-isoprenaline, (R)-norfluoxetine and (R)-fluoxetine

An efficient asymmetric synthesis of enantiomerically pure (R)-isoprenaline, (R)-norfluoxetine and (R)-fluoxetine is described using Sharpless asymmetric dihydroxylation as the key step.     

Synthesis of conjugated (1E,3E)- and (1Z,3Z)-1,4-di(n-pyridyl) (or n-quinolyl)-1,3-butadienes from n-(2′-chloroethenyl)pyridine (or quinoline)

The homocoupling reaction between the conjugated n-(2-chloroethenyl)pyridine; n, 2-, 3- and 4- (or quinoline; n, 2- and 4-) mediated by zero-valent nickel complexes at room temperature affords to the corresponding 1,4-diaryl-1,3-butadiene, always as the 1E,3E stereoisomer. The yield in 1,4-diaryl-1,3-butadiene increases with the nickel catalyst and hence, the active zero-valent nickel catalyst is not regenerated during the homocoupling reaction.The stereospecific synthesis of (1Z,3Z)-1,4-di(4′-pyridyl)-1,3-butadiene stereoisomer was efficiently carried out by partial hydrogenation of the appropriate 1,4-di(4′-pyridyl)-1,3-butadiyne.     

Stereoselective synthesis of vinylic (Z)-vic-bis(arylchalcogenides)

Alkyne-titanium complexes 3, readily prepared in situ by the reaction of alkynes with Ti(O-i-Pr)₄/2 i-PrMgCl, react with electrophilic chalcogen species under mild conditions to provide the corresponding addition products in fair to good yields. The obtained vinylic vic-bis(arylchalcogenides) 4 are useful synthetic intermediates for introducing vinyl functions into organic molecules.     

Stereoelective radical copolymerization of (RS)-α-methylbenzyl vinyl ether with (S)-(-)- or (R)-(+)-N-(α-methylbenzyl)maleimide

Racemic α-methylbenzyl vinyl ether was copolymerized with optically active (S)-(-)- or (R)-(+)-N-(α-methylbenzyl)maleimide using 2,2′-azobisisobutyronitrile in order to examine the possibility of stereoelective radical polymerization of vinyl-type racemic monomers. The resulting copolymers were found to have almost alternating sequences of the two kinds of monomeric units. The non-polymerized α-methylbenzyl vinyl ether, recovered from the copolymerization system, showed an optical activity of opposite sign to the optically active comonomer used, indicating clearly that the co-polymerization process is stereoelective. It was confirmed that α-methylbenzyl vinyl ether preferentially incorporated in the copolymer has the same absolute configuration as the optically active N-substituted maleimide.