Syntheses, properties and structures of copper and nickel complexes of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate

The reaction of CuCl2-2H2O or NiCl2.6H2O with K2(C5H6S4) [potassium salt of 6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate] under nitrogen atmosphere resulted in the isolation of [Cu(C5H6S4)2]- or [Ni(C5H6S4)2]- as the tetrabutylammonium salt. Both complexes show characteristic IR and UV-Vis absorptions of transition metal dithiolenes. Cyclic voltammograms contain two waves indicating a two step electrochemical procedure [M(C5H6S4)2]0 = [M(C5H6S4)2]1-= [M(C5H6S4)2]2-. Single crystal structure study has been carried out on the nickel complex. Crystal of [Bu4N][Ni(C5H6S4)2] belongs to monoclinic space group P21/c with a=17.576(5), 6=10.883(2), c=17.773(4) A,B=91.07(2)0, Z=4, and o(calcd.)=1.348 g/cm3. Final result is R=0.059 for 2959 reflections. The NiS4 core exhibits square planar coordination with average Ni-S bond length of 2.134(5) A. There are not anion pairs in crystal. The anions stack along a and c axes while the cations intercalate in them. The nearest S-S contact is 4.429 A. The solid powder ESR s     

聚-4,7-二硫杂壬基倍半硅氧烷铂配合物的合成及其对烯烃硅氢加成反应的催化性能

4,7-二硫杂壬基三甲氧基硅烷以气相法二氧化硅固载化,再与氯亚铂酸钾反应,合成了气相法二氧化硅固载的聚-4,7-二硫杂壬基倍半硅氧烷铂配合物。该配合物用量为烯烃摩尔数十万分之一时,仍能有效地催化烯烃与三乙氧基硅烷的硅氢加成反应,单程烯烃转化数可达80,000。     

[(C~8H~8)Y(μ-OC~6H~5)(THF)]~2的合成和晶体结构

本文用(C~8H~8)Y(μ-Cl)(THF)]~2与NaOC~6H~5以1:2摩尔比在四氢呋喃中反应, 合成了新的中性配合物[(C~8H~8)Y(μ-OC~6H~5)(THF)]~2, 经过分离, 在-30℃下培养得到无色晶体, 用元素分析, 核磁共振和质谱进行了鉴定, 并以X-射线衍射测定了晶体结构。     

Encapsulating property of ap-t-butylcalix[6]arene derivative: Formation of charge-transfer complexes of alkadienes with iodine in the presence of octopus-type calix[6]arene

This paper deals with the ability ofp-tert-butylcalix[6]arene derivative1, which has six 3,6,9-trioxadecyl substituents at the phenolic oxygens, to encapsulate CT complexes of alkadienes with iodine. By adding I₂ to alkadienes in CH₂Cl₂ in the presence of1, the absorbance at 363 nm, which was ascribed to I ₃ ^– ion, increased in the order: 1,5-hexadiene<1,9-decadiene 1,7-octadiene. The reactivity features of the CT complexes in the presence of1 are discussed.     

Counterpoise技术和He-H2O配合物的平衡几何

在得到MP4, SCF的关于总能量及结合能的四个势能面的基础上,着重分析了电子相关作用, 消除基函数超位误差的Counterpoise(CP)技术对van der Waals配合物He-H2O的平衡几何的影响并得到了更精确的平衡几何预测。     

含稀土铕(Ⅲ)配位聚合物的研究

将铕的有机配合物NaEu(TTA)4与聚（苯乙烯-丙烯酸）（PSAA）反应制备了铕配位聚合物[Eu(Ⅲ）-TTA-PSAA]，用电导、DTA-TGA、荧光光谱等对其进行了表征。由于配合物中存在着Eu^3 分别与TTA^-和PSAA分子中羧基的配位作用，并进一步交联，因此配合物样品均不溶于大部分有机溶剂，只能溶于N，N-二甲基甲酰胺和丙三醇/异丙醇的混合溶剂，且耐热性得到提高。配合物为褐色固体，在常温、紫外光下发出红光，主要是由于Eu^3 离子的^5D0→^7F2跃进。讨论了pH值对配合物荧光强度的影响，当pH=10时，合成的配合物具有最好的荧光性。     

Synthesis of Two Novel Rhenium（I） Bipyridyl Photosensitive Dyes

Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN.     

7─羟基喹啉与甲醇、乙醇形成1：2桥式氢键化合物的AM1法研究

利用半经验ＡＭ１方法计算了基态与第一激发态７－羟基喹啉的两种异构体及其与甲醇等溶济分子形成１：２桥式氢键化合物的结构与稳定性。在基态，烯醇式结构比酮式结构稳定；而在第一激发态酮式比烯醇式稳定。１：２桥式氢键的形成使得酮式能量降低比烯醇式多。烯醇式１：２桥式氢键化合物呈交叉式结构，酮式１：２桥式氢键化合物呈折叠式结构，激发态的形成对氢键结构影响不大。在７－羟基喹啉羟基（或羰基）的邻位和间位引入取代基后，对喹啉环和桥式氢键结构的影响均不明显。     

含N-苯甲酰皮考林酰肼的钒酰、镍及锰配合物的合成和晶体结构

合成了3个含N-苯甲酰皮考林酰肼(简写为HL)的钒、镍和锰配合物[VO_2L](1,C_(13)H_(10)N_3O_4V,M_r=323.18),[NiL_2]·0.5CH_3OH(2,C_(26.5)H_(22)N_6NiO_(4.5),Mr=555.21)和[MnL_2]·0.5CH_3OH(3,C_(26.5)H_(22)MnN_6O_(4.5),Mr=551.44)。配合物1属三斜晶系,空间群为P1,a=0.71241(3)nm,b=0.89625(6)nm,c=1.11706(6)nm,α=94.715(2)°,β=102.053(2)°,γ=112.375(3)°,V=0.63461(7)nm~3,Z=2,F(000)=328,μ(MoKα)=0.802mm~(-1),R=0.0290,wR=0.0816;配合物2属单斜晶系,空间群为C2/c,a=2.5875(1)nm,b=1.4868(1)nm,c=1.8353(1)nm,β=134.470(4)°,V=5.2081(5)nm~3,Z=8,F(000)=2368,μ(MoKα)=0.795mm~(-1),R=0.0459,wR=0.1330;配合物3属单斜晶系,空间群为C2/c,a=2.60113(3)nm,b=1.45231(4)nm,c=1.92903(1)nm,β=132.824(1)°,V=5.3448(2)nm~3,Z=8,F(000)=2344,μ(MoKα)=0.543mm~(-1),R=0.0457,wR=0.1325。在配合物1中,钒(V)原子具有畸变的N_2O_3四角锥配位构型,晶体内每两个分子通过分子间氢键作用形成缔合分子对。在配合物2和配合物3中,镍(Ⅱ)原子和锰(Ⅱ)原子具有扭曲的N_4O_2八面体配位构型,晶体通过分子间氢键作用形成一维的无限链状结构。红外光谱表明,配体在形成配合物后,ν(C=O)和ν(C=N)红移。电     

Nanorods of Various Oxides and Hierarchically Structured Mesoporous Silica by Sol-Gel Electrophoresis

In this paper, we report the template-based growth of nanorods of oxides and hierarchically structured mesoporous silica, formed by means of a combination of sol-gel processing and electrophoretic deposition. Both single metal oxides (TiO₂) and complex oxides (Pb(Zr_0.52Ti_0.48)O₃) have been grown by this method. This method has also been applied to the growth of nanorods of mesoporous silica having an ordered pore structure, where the pores are aligned parallel to the long axis of the nanorod. Uniformly sized nanorods of about 125–200 nm in diameter and 10 m in length were grown over large areas with near unidirectional alignment. Appropriate sol preparation yielded the desired stoichiometric chemical composition and crystal structure of the oxide nanorods, with a heat treatment (500–700°C for 15–30 min) for crystallization, densification and any necessary pyrolysis.