两种单齿硫醇为配位体的钼络合物的合成和结构表征

本文报导利用MoC1_5、NaOMe、C_6H_5CH_2SH和NaHS在无氧、无水,室温条件下在甲醇介质中合成(Et_4N)_2[Mo_2O_2S_2(SCH_2C_6H_5)_4](化合物Ⅰ)和(Et_4N)-[Mo_2O_2(μ-SCH_2C_6H_5)_3(SCH_2C_6H_5)_4](化合物Ⅱ)的反应条件,分离步骤。本文同时报导这两种化合物的核磁共振谱、红外光谱、电子光谱等结构表征,同时也对化合物形成的可能机理作了探索性的讨论。     

不同质量Cn笼电子结构和UV谱的理论研究

用INDO/2和INDO/CI方法研究了C_(24)、C_(50)、C_(60)和C_70的电子结构和UV谱。稳定性的顺序为C_(60)～C_(70)>C_(50)>>C_(24)。以C_(60)为中心向两边的C_n原子簇,其UV谱发生红移。     

紫外激光诱导C60与M(CO)6(M=Cr,Mo, W)的配位反应

研究了用紫外激光(355 nm)诱导C_(60)与金属羰基化合物M(CO)_6(M＝Cr；Mo，W)的配位反应，合成了具有C_(4υ)对称性的配位络合物(η~2－C_(60))M(CO)_5，并初步讨论了C_(60)与M(CO)_6反应的动力学过程．     

C60系列化合物的磁学性质

本文概述了C_(60)系列化合物的NMR谱、磁化率、磁性的某些进展。     

富勒烯吡咯金属配合物的合成、表征及光电性能

采用肌氨酸甲酯(CH_3NHCH_2COOMe)与C_(60)光化学反应制得富勒烯吡咯衍生物(C_(60)Pyr),产率为67％(基于已反应的C_(60)),并以其为配体,在N_2气气氛下利用配体取代法合成了富勒烯吡咯金属配合物(PyrC_(60))-Pd(dppe),产率为51％(基于C_(60)吡咯衍生物)。采用元素分析、质谱、紫外-可见吸收光谱、红外光谱、X射线光电子能谱和核磁共振(~(31)P NMR)等测试技术对中间物及产物进行了表征,同时在光电化学电池中于GaAs电极上测量了化合物(PyrC_(60))-Pd(dppe)的光伏效应(PVE),研究了介质电对、配合物薄膜厚度对光电性能的影响。研究结果表明,(PyrC_(60))-Pd(dppe)/GaAs电极的值比单纯的GaAs电极的ΔV和ΔI相应值大得多,这种化合物具有优良的光电性能。尤其在O_2/H_2O介质电对中,光生电压值最大可达230 mV,光生电流最大可达8．7μA。镀层厚度在0．5～1μm时,光伏效应值较大。     

C60衍生物的MALDI-TOFMS分析

C_(60)衍生物在超导、非线性光学、催化、材料和生物活性等方面有巨大的潜在应用价值。C_(60)衍生物大多为固体,蒸汽压较低,采用需要加热才能够使样品气化电离的质谱或"硬"电离质谱方法进行测定,易造成C_(60)衍生物分解并释放出配体。近年来国内外应用基体辅助激光解吸软电离质谱法成功分析了许多不同类型的C_(60)衍生物如卤化C_(60)酰胺化C_(60)芳基化C_(60)、C_(60)部花菁、煤基C_(60)烟灰萃取产物、金属C_(60)衍生物以及C_(60)乙二胺膜等。本文报道采用MALDI-TOFMS法分析C_(60)酯衍生物和C_(60)吡咯烷衍生物的结果。     

烯丙胺与C_(60)的热引发[3+2]环加成反应

烯丙胺类化合物与C_(60)在热引发下发生新型的[3+2]环加成反应。反应有较 好的立体选择性。该反应可能经过了热引发的烯丙胺的单电子转移过程，产生烯丙 基自由基，并进一步与C_(60)加成及环化。文中C_(60)衍生物的结构均经过谱学方 法确证。     

硼化合物的研究——Ⅺ.氢硼酸π-环戊二烯基-烷撑双(二苯基膦)合镍(Ⅱ)的合成和性质

本文以C_5H_5NiPPh_3Cl与Ph_2P(CH_2)_nPPh_2为起始物合成了C_5H_5NiPh_2P(CH_2)nPPh_2Cl·C_6H_6,再进一步与氢硼酸季铵盐反应,合成了12个氢硼酸π-环戊二烯基-烷撑双(二苯基膦)合镍(Ⅱ)化合物。对这些化合物进行了元素分析、红外光谱鉴定,并测定了氯化物的~1H NMR谱。所有含硼化合物于室温下对空气是稳定的,而它们的热稳定性与阳离子中螯合环的大小和氢硼酸根结构有关,即氢硼酸根相同的化合物,热稳定性随着螯合环的增大而降低;阳离子相同时,热稳定性次序是:[C_5H_5NiPh_2P(CH_2)_nPPh_2]_2B_(12)H_(12)>[C_5H_5NiPh_2P(CH_2)_nPPh_2]_2B_(10)H_(10)>C_5H_5NiPh_2P(CH_2)_nPPh_2B_(11)H_(14)>C_5H_5NiPh_2P(CH_2)_nPPh_2B_3H_8。     

与二茂铁酰基相连的螺噁嗪的合成、结构及性质

在二环已基碳二亚胺(DCC)存在下, 将9′-羟基螺噁嗪与二茂铁甲酸进行酯化缩合, 合成了一种与二茂铁酰基相连的螺噁嗪衍生物2, 用核磁共振氢谱、碳谱、红外光谱、高分辨质谱和X射线单晶衍射对其结构进行了表征. 化合物2在几种有机溶剂中都表现出了良好的光致变色性质; 通过实验证明了在无冰水浴冷却条件下, 用高压汞灯照射时化合物2在二氯甲烷中表现出的特殊变色性是酸致变色的结果; 同时还研究了化合物2在固体PMMA薄膜中的光致变色性质. 在高压汞灯照射下,化合物2在二氯甲烷溶液中显示了良好的荧光性. 循环伏安法测定结果表明化合物2具有良好的氧化还原可逆性.     

取代戊二烯Ti,V羰基化合物的谱学研究

利用IR，EPR和UV-VIS方法对系列取代戊二烯基钛，钒羰基化合物进行了表征，用EHMO方法对开环夹心化合物[2,4-(CH_3)_2C_2H_5]_2VCO和开、闭环夹心化合物[2,4(CH_3)_2C_5H_5](C_5H)5)VCO进行了计算，对开环夹心羰基化合物，开、闭环夹心羰基化合物及闭环夹心羰基化合物进行了比较．结果表明，开、闭环夹心羰基化合物的性质介于开环夹心羰基化合物和闭环夹心羰基化合物之间，且更接近于开环夹心羰基化合物，开环配体与Ti，V间的化学键较强，对于化合物性质影响较大．     

Synthesis, optical properties, and LFER analysis of solvent-dependent binding constants of Hamilton-receptor-connected merocyanine chromophores

A merocyanine dye equipped with a Hamilton-receptor unit has been synthesized that enables strong noncovalent binding of other merocyanine dyes bearing barbituric acid acceptor groups by six hydrogen bonds. NMR and UV/vis titration experiments in toluene, chloroform, dichloromethane, dioxane, and THF provide evidence for the formation of 1:1 complexes even in the dipolar solvents. An enhanced binding strength is observed for the more dipolar merocyanine dyes in the head-to-tail assembly structure with binding constants up to >10 (8) M (-1) in toluene. In the present bimolecular complexes two merocyanine chromophores are assembled in a head-to-tail fashion that affords increased dipole moments as demanded for efficient electric field induced poling processes in nonlinear optical and photorefractive polymeric hosts. The solvent dependency of the binding constants for various barbituric acid dye-Hamilton receptor complexes as well as a perylene imide-melamine complex reveals linear free energy relationships (LFER) that allow for an estimation of binding constants larger than 10 (12) M (-1) for Hamilton receptor organized head-to-tail merocyanine bimolecular complexes in aliphatic solvents. It is suggested that such LFER are valuable tools for the estimation of binding constants in solvents where experimental binding constants cannot be determined because of solubility or spectroscopic problems.     

变色硅胶吸附脱除模拟柴油中各种碱性氮化物

研究了变色硅胶吸附脱除氮含量为960.56μg/g模拟柴油中的碱性氮化物喹啉、苯胺和吡啶。比较了氧化铝、硅藻土、硅胶及变色硅胶对模拟柴油中喹啉的吸附脱除效果。采用XRD、低温N_2吸附-脱附和NH_3-TPD等方法对硅胶和变色硅胶进行了表征。考察了粒径、吸附温度、吸附时间、剂油质量比及共存芳香化合物(萘、苯或甲苯)对变色硅胶吸附脱除各种碱性氮化物的影响。变色硅胶吸附脱除碱性氮化物的顺序均为苯胺吡啶喹啉。吸附时间对三种氮化物的吸附脱除没有影响;吸附温度、变色硅胶粒径和共存芳香化合物对苯胺和吡啶的吸附脱除效果影响不大,对喹啉的吸附脱除效果影响较为明显;剂油质量比对三种氮化物的吸附脱除影响均较大,尤其是对喹啉影响最大。结果表明,变色硅胶吸附各种氮化物时Co能够与其中的N原子形成配位络合吸附。经焙烧再生,变色硅胶几乎完全恢复了对喹啉和吡啶的吸附脱除能力,并可多次再生,但变色硅胶再生后对苯胺的吸附能力损失较大。     

Syntheses and some spectroscopic properties of polyanions with pendant merocyanine dyes

Polymers tagged with a local pH reporter were synthesized. A methacrylate-type monomer containing a merocyanine dye residue as a reporter dye—1-(2-methacryloyloxyethyl)-4-(2-(4-hydroxyphenyl)-ethenyl)quinolinium bromide—was synthesized. Its homopolymer and copolymers with sodium 2-acrylamido-2-methylpropanesulfonate were prepared by free radical polymerization. These polymers showed a characteristic color change in aqueous solutions from yellow to red with increasing pH from acidic to basic conditions according to the acid-base equilibria of the merocyanine dye residues. Since the electrostatic potential and polarity of media have a strong effect on the acid–base equilibria, the pendant merocyanine residues are expected to serve as a reporter to provide information on the local environments around the polymer chain at which the dye molecules are incorporated.     

Photosensitive cholesteric copolymers with spiropyran-containing side groups I. Phase behaviour and photo-optical properties

A number of terpolymers were synthesized by copolymerization of nematogenic, chiral and photochromic monomers with different contents of spiropyran photosensitive side groups. The synthesized copolymers possess selective light reflection in the visible region of the spectrum. Action of UV light on planarly-oriented films of the copolymers leads to the formation of the merocyanine form of the dye with a maximum of absorbance coinciding with the selective light reflection peak. The 'degeneration' of the selective light reflection is observed during this process. It was shown that such types of material can be used for reversible information storage; the principal scheme for the processes of optical data recording and reading is suggested.     

Merocyanine dye-sensitized photoconductivity of polymer composites based on heterometallic copper/iron complexes

The electric and photoconductive properties of films of polymer composites containing heterometallic complexes [Cu(phen)₂Fe(CN)₅NO]· 2H₂O or [Cu(phen)₂Br]₂[Fe(CN) ₅NO]DMF (where phen is 1,10-phenanthroline and DMF is dimethylformamide) and a merocyanine dye were studied. The photocurrent is greater for the bromide complex and increases upon introduction of a merocyanine dye into the composites. The photocurrent also increases upon the application of an external magnetic field and saturates in fields of <1 kOe. It is assumed that the sensitization of photoconductivity by the merocyanine dye is due to photogeneration of triplet charge pairs from dye molecules and transport of nonequilibrium charge carriers in and between the particles of the complexes, rather than to an increase in the absorbance.     

Photosensitive cholesteric copolymers with spiropyran-containing side groups I. Phase behaviour and photo-optical properties

A number of terpolymers were synthesized by copolymerization of nematogenic, chiral and photochromic monomers with different contents of spiropyran photosensitive side groups. The synthesized copolymers possess selective light reflection in the visible region of the spectrum. Action of UV light on planarly-oriented films of the copolymers leads to the formation of the merocyanine form of the dye with a maximum of absorbance coinciding with the selective light reflection peak. The 'degeneration' of the selective light reflection is observed during this process. It was shown that such types of material can be used for reversible information storage; the principal scheme for the processes of optical data recording and reading is suggested.     

Photogeneration of holes and electrons in amorphous molecular semiconductors with neutral and ionic organic dyes

Photoconducting properties of amorphous molecular semiconductors based on polystyrene films doped with tetranitrofluorenone and merocyanine or an anionic polymethine dye, or with epoxypropylcarbazole and merocyanine or a cationic polymethine dye were studied. The former type of the films is characterized by electron conductivity, whereas the latter type by hole conductivity. The activation energy for photogeneration of mobile charge carriers increases on passing from a merocyanine dye to ionic dyes and decreases with a growth in quantum energy of excitation light for the films of the former type, but does not depend on the light quantum energy for the films of the latter type. It was concluded that the activation energy of photogeneration is determined by electrostatic interaction of a photogenerated charge carrier with the ionized photogeneration site or a counterion for neutral and ionic dyes, respectively. At low dissipation rates of the excess thermal energy of excited dye molecules via electron-nucleus interaction, photogenerated electrons have a possibility to travel over a long distance from the photogeneration site as compared with holes.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 3, 2005, pp. 195–203.Original Russian Text Copyright © 2005 by Davidenko, Derevyanko, Zabolotnyi, Ishchenko, Kuvshinskii, Studzinskii.     

Spectroscopic characterization of Brooker’s merocyanine in Silicalite-1 and ZSM-5 leading to second harmonic generation

The use of porous materials has become increasingly significant in the pursuit of novel composite materials with nonlinear optical properties. The microporous channels in Silicalite-1 and ZSM-5, which have identical crystal frameworks but different chemical composition, were used to study the role of zeolite composition on dye adsorption and organization, leading to second-harmonic generation (SHG). The dye molecule, known as Brooker’s merocyanine (4-[(1-methyl-4(1H)-pyridinylidene)ethylidene]-2,5-cyclohexadien-1-one), exhibits one of the largest known molecular hyperpolarizabilities for small dye molecules, but it crystallizes centrosymmetrically. When Brooker’s merocyanine was adsorbed to Silicalite-1 powder, no SHG was detected, but when adsorbed to ZSM-5, the powder was SHG-active. Spectroscopic characterization of the new materials was used to determine the dye loading in each zeolite. The hydrophilic ZSM-5 channels proved to be essential for dye adsorption and alignment within the channels as compared to the hydrophobic Silicalite-1 which did not appreciably adsorb the dye. The effect of dye protonation and isomerization on adsorption to each zeolite was also studied, with neither having an effect on the amount of dye adsorbed.     

一种含螺吡喃和肉桂酸酯双光功能基团的光致变色染料的合成与性能

合成了一种含有光致聚合肉桂酸酯基团的新型光致变色螺吡喃染料,研究其与普通螺吡喃染料在不同高分子材料中的光致变色和热退色过程(PMMA和PVCi).通过UV-Vis光谱、NMR谱和IR光谱研究了新型染料中的肉桂酸酯基团的光致聚合过程,考察了其对螺吡喃结构的光致变色显色体热稳定性的影响.     

Comparison of the reactivity of isomeric 2H- and 3H-naphthopyran mechanophores

Naphthopyrans are molecular switches that produce highly colored merocyanine dyes upon photochemical or mechanochemical activation in polymers. The mechanochromic behavior of these molecular force probes enables the straightforward visualization of stress and/or strain in materials. To date, research on the mechanochemistry of naphthopyran has largely focused on the 3H-naphtho[2,1-b]pyran (3H) scaffold, whereas isomeric 2H-naphtho[1,2-b]pyrans (2H) exhibit complementary properties as suggested from their photochemical reactivity. Here we directly compare the reactivity of two isomeric 2H- and 3H-naphthopyran mechanophores in solution-phase ultrasonication experiments and in crosslinked polydimethylsiloxane elastomers subjected to uniaxial tensile deformation. The prototypical 3H-naphthopyran mechanophore produces a yellow merocyanine dye that reverts quickly, while the 2H-naphthopyran mechanophore generates a red merocyanine dye that reverts significantly slower. The trends in absorption and reversion measured in solution are also reflected in solid polymeric materials activated in tension. Building on recent research into substituent effects, this study identifies naphthopyran isomerism as a simple lever for modulating the mechanochromic properties of the naphthopyran mechanophore used in the development of force-responsive polymers.