配位聚合物[HgI_2(bpea)]_n[bpea=1,2-双(4-吡啶基)乙烷]的合成结构表征和光学折射效应(英文)

制备44连吡啶基二卤加和物MX244′bipyn仍然有较大困难。这类化合物数量不多且已报道的多为难处理的微晶材料。本文在室温下通过简单的操作合成了新的碘化汞连吡啶乙烷加和物HgI2bpean。X射线单晶衍射分析表明其中的汞原子通过与两个碘原子以及吡啶乙烷的两个氮原子配位形成扭曲的四面体构型。每个HgI2单元由bpea桥连形成锯齿状链。其非线性光学性质用8纳秒激光在532nm波长进行了研究。该化合物相对于入射光表现为一定的光学吸收和强的自聚焦效应,其三阶非线性吸收系数α2=1.1×10-11m·W-1折射系数n2=5.29×10-18m2·W-1。     

配位聚合物[HgI2(bpea)]n[bpea=1,2-双(4-吡啶基)乙烷]的合成结构表征和光学折射效应

制备4,4-连吡啶基二卤加和物[MX2(4,4′-bipy)]n仍然有较大困难.这类化合物数量不多且已报道的多为难处理的微晶材料.本文在室温下通过简单的操作合成了新的碘化汞连吡啶乙烷加和物[HgI2(bpea)]nox-射线单晶衍射分析表明其中的汞原子通过与两个碘原子以及吡啶乙烷的两个氮原子配位形成扭曲的四面体构型.每个HgI2单元由bpea桥连形成锯齿状链.其非线性光学性质用8-纳秒激光在532nm波长进行了研究.该化合物相对于入射光表现为一定的光学吸收和强的自聚焦效应,其三阶非线性吸收系数α2=1.1×10-11m@W-1,折射系数n2=5.29×10-188m2@w-1.     

簇合物[WS_4Ag_3(PPh_3)_3{S_2P(OCH_2Ph)_2}]的合成、晶体结构及非线性光学性质

本文用(NH4)2WS4,Ag犤S2P(OCH2Ph)2犦和PPh3为原料合成了簇合物犤WS4Ag3(PPh3)3狖S2P(OCH2Ph)2狚犦,并得到了晶体。晶体属正交晶系,空间群为P212121,晶胞参数a=1.32370(4)nm,b=1.34427(4)nm,c=3.83246(11)nm。X-射线单晶结构测定结果表明它具有巢状分子结构,配体(PhCH2O)2PS2-(简称dtp)的两个S原子中的一个硫原子仅与一个金属原子配位,另一个硫原子则同时与两个金属原子配位。簇合物的非线性光学性质用脉宽8ns激光在532nm波长进行了研究。该化合物表现为一定的光学吸收和强的自聚焦效应,其三阶非线性吸收系数α2=1.50×10-10m·W-1,折射系数n2=2.45×10-11esu。     

停止-流动分光光度法研究铕(II)与二甲酚橙快速电子转移反应动力学

用停止-流动分光光度法研究了Eu~(2+)与二甲酚橙(XO)间快速电子转移反应的动力学规律。求得了速控步骤的动力学参数。如反应级数(n=2)、几个不同温度下的速率常数(k_(278 K)=5.7×10~8 L·mol~-·s~(-1), k_(s38 K)=1.01×10~9 L·mol~(-1)·s~(-1))、活化能(E=7.6×10~3 J·mol~(-1)), 以及指前因子(A=1.5×10~(10) L·mol~(-1)·s~(-1)), 并判断出其为溶液中扩散控制型反应。根据实验现象与测试结果, 提出了Eu~(2+)与XO的反应分别在Eu~(2+)相对过量和在XO过量时的反应机理, 并判断了各反应步骤速率常数之间的相对关系。     

停止-流动分光光度法研究铕(Ⅱ)与二甲酚橙快速电子转移反应动力学

用停止-流动分光光度法研究了Eu~(2+)与二甲酚橙(XO)间快速电子转移反应的动力学规律。求得了速控步骤的动力学参数。如反应级数(n=2)、几个不同温度下的速率常数(k_(278K)=5.7×10~8L·mol~-·s~(-1),k_(s38K)=1.01×10~9L·mol~(-1)·s~(-1))、活化能(E=7.6×10~3J·mol~(-1)),以及指前因子(A=1.5×10~(10)L·mol~(-1)·s~(-1)),并判断出其为溶液中扩散控制型反应。根据实验现象与测试结果,提出了Eu~(2+)与XO的反应分别在Eu~(2+)相对过量和在XO过量时的反应机理,并判断了各反应步骤速率常数之间的相对关系。     

2-(5-溴-2-吡啶偶氮)-5-二乙氨基酚与铅(Ⅱ)、锌(Ⅱ)络合平衡的双系列线性回归法研究

本文用双系列线性回归法研究了Pb(Ⅱ)、Zn(Ⅱ)与5-Br-PADAP的络合反应,发现在pH5～6.5,30％乙醇溶液中,Pb(Ⅱ)与5-Br-PADAP形成1:1络合物,Zn(Ⅱ)主要形成1:2络合物,两种络合物的稳定常数(lgβ)分别为11.17、22.31,最大吸收波长分别为575、550nm,摩尔吸光系数分别为6.01×10~4、1.34×10~5L·mol~(-1)·cm~(-1)。     

贵金属高灵敏显色反应的研究(Ⅰ) 金(Ⅲ)-碘化钾-丁基罗丹明B-明胶体系

贵金属已知的显色反应中,除萃取浮选的以外,摩尔吸光系数(ε)达到或超过2×10~5I·mol~(-1)·cm~(-1)者为数甚少。就金来说,目前以乙基硫代米嗤酮的灵敏度最高(ε=1.95×10~5l·mol~(-1)·cm~(-1)),甲基硫代米嗤酮次之(ε=1.6×10~5l·mol~(-1)·cm~(-1))。碱性染料如罗丹明B与AuCl_4~-缔合萃取显色反应ε=9.7×10~4l·mol~(-1)·cm~(-1)。有关金(Ⅲ)-碘化钾-碱性染料体系显色反应仍未见报道。我们发现在明胶、TritonX-100和抗坏血酸存在下Au(Ⅲ)与KI、罗丹明B特别是丁基罗丹明B的显色反应具有很高的灵敏度,有色络合物的摩尔吸光系数分别为2.3×10~5l.mol~(-1)·cm~(-1)(罗丹明B)和1.2×10~6l·mol~(-1)·cm~(-1)(丁基罗丹明B),特别是后者,ε值之高实属罕见,故我们称之为超高灵敏显色反应。     

在二甲基亚砜-丙酮-水溶液中硫氰酸钼(Ⅴ)络合物的研究

本文采用分配法研究了二甲基亚砜-丙酮-水溶液中硫氰酸钼(V)络合物的性质。三个络合物MoO(SCN)~(2+),MoO(SCN)_2~+和MoO(SCN)_3的稳定常数分别为β_1=46.1,β_2=1040,β_3=12259,其各级络合物的摩尔吸光系数分别是△ε_1=0.59×10~4L·mol~(-1)·cm~(-1),△ε_2=0.94×10~4L·mol~(-1)·cm~(-1)和△ε_3=1.4×10~4L·mol~(-1)·cm~(-1),研究了该络合物的生成机理,发现以CCI_4,为萃取剂效果不好,如在CCI_4中加入少量溴化十六烷基三甲基铵后萃取效果与前人使用CHCI_3相类似。     

铈(Ⅳ)-吐温40-对苯二酚化学发光体系测定氢醌乳膏中对苯二酚

讨论了表面活性剂对铈(Ⅳ)氧化对苯二酚化学反应的影响,发现了铈(Ⅳ) 吐温40 对苯二酚化学发光新体系,建立了测定对苯二酚化学发光分析方法,该法测定对苯二酚的线性范围为8.0×10-7～5.0×10-5mol·L-1,检出限为5.0×10-7mol·L-1,相对标准偏差为2.5%(5.0×10-6mol·L-1对苯二酚,n=11)。该法应用于测定氢醌乳膏中的对苯二酚,结果满意。     

N-甲基吡咯烷酮与H_nXW_(12)O_(40)·mH_2O(X=P,Si,Ge)电荷转移盐的合成、表征及非线性光学性质研究

由N -甲基吡咯烷酮和HnXW1 2 O40 ·mH2 O(X =P ,Si,Ge)合成了具有非线性光学性质的电荷转移盐 ,(NMPH) 3PW1 2 O40 ·CH3CN(I) ,(NMPH) 4 SiW1 2 O40 ·CH3CN(Ⅱ )和 (NMPH) 4 GeW1 2 O40 ·CH3CN(Ⅲ ) .并由元素分析 ,红外光谱 ,漫反射电子光谱进行了表征。结果表明杂多酸形成电荷转移盐后其阴离子结构未变 ;N -甲基吡咯烷酮通过N原子与酸中的质子H+结合成阳离子而成盐 ,光激发下阴阳离子之间可以发生电荷转移 ,非线性光学性性质研究表明 ,电荷转移盐的倍频效应强度分别为I2ωⅠ =0 .6IKDP,I2ωⅡ =0 .85和I2ωⅢ =0 .41IKDP,三阶非线性系数分别为 χ(3)Ⅰ =1 .60× 1 0 - 1 2 esu ,χ(3)Ⅱ =3.6× 1 0 - 1 2 esu ,χ(3)Ⅲ =1 .2× 1 0 - 1 1 esu .     

层状配位聚合物犤Pb(NCS)2(bpea)n的合成,结构和非线性光学性质(bpea=1,2-双(4-吡啶基)乙烷)

室温下Pb(OAC)     

New Ru complexes containing the N-tridentate bpea and phosphine ligands: consequences of meridional vs facial geometry

The synthesis and isolation of the complex cis,fac-[RuIICl2(bpea)(PPh3)][3; bpea = N,N-bis(2-pyridylmethyl)ethylamine] and three geometrical isomers of the complex [RuIICl(bpea)(dppe)](BF4) [4; dppe = (1,2-diphenylphosphino)ethane], trans,fac (4a), cis,fac (4b), and mer(down) (4c), have been described (see Chart 1 for a drawing of their structures). These complexes have been characterized through analytical, spectroscopic (IR, UV/vis, and 1D and 2D NMR), and electrochemical (cyclic voltammetry) techniques. In addition, complexes 3, 4a, and 4b have been further characterized in the solid state through monocrystal X-ray diffraction analysis. The molecular and electronic structures of isomers 4a, 4b, 4c, and 4d (the mer(up) isomer) have also been studied by means of density functional theory (DFT) calculations. Furthermore, their low-energy electronic transitions have been simulated using time-dependent DFT approaches, which have allowed unraveling of their metal-to-ligand charge-transfer nature. Complexes 3 and 4a-c are capable of catalyzing H-transfer types of reactions between alcohols and aromatic ketones such as acetophenone and 2,2-dimethylpropiophenone (DP). A strong influence of the facial versus meridional geometry in the bpea ligand coordination mode is observed for these catalytic reactions, with the meridional isomer being much more active than the facial one. The meridional isomer is even capable of carrying out the H-transfer reaction of bulky substrates such as DP at room temperature.     

Synthesis, structure, and redox and catalytic properties of a new family of ruthenium complexes containing the tridentate bpea ligand

We have prepared a new family of ruthenium complexes containing the bpea ligand (where bpea stands for N,N-bis(2-pyridyl)ethylamine), with general formula [Ru(bpea)(bpy)(X)](n+) (2, X = Cl(-); 3, X = H(2)O; 4, X = OH(-)), and the trisaqua complex [Ru(bpea)(H2O)(3)](2+), 6. The complexes have been characterized through elemental analyses, UV-vis and (1)H NMR spectroscopy, and electrochemical studies. For complex 3, the X-ray diffraction structure has also been solved. The compound belongs to the monoclinic P2(1)/m space group, with Z = 2, a = 7.9298(6) A, b = 18.0226(19) A, c = 10.6911(8) A, and beta = 107.549(8) degrees. The Ru metal center has a distorted octahedral geometry, with the O atom of the aquo ligand placed in a trans position with regard to the aliphatic N atom of the bpea ligand so that the molecule possesses a symmetry plane. NMR spectra show that the complex maintains its structure in aqueous solution, and that the corresponding chloro complex also has a similar structural arrangement. The pH dependence of the redox potential for the complex [Ru(bpea)(bpy)(H2O)](PF(6))(2) is reported, as well as the ability of the corresponding oxo complex to catalyze the oxidation of benzylic alcohol to benzaldehyde in both chemical and electrochemical manners.     

OH(3) (-) and O(2)H(5) (-) double Rydberg anions: predictions and comparisons with NH(4) (-) and N(2)H(7) (-)

A low barrier in the reaction pathway between the double Rydberg isomer of OH(3) (-) and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH(4) (-). Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH(3) (-) DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O(2)H(5) (-) species. Three O(2)H(5) (-) minima with H(-)(H(2)O)(2), hydrogen-bridged, and DRA-molecule structures resemble previously discovered N(2)H(7) (-) species and have well separated VEDEs that may be observable in anion photoelectron spectra.