Combined Transient Spectra and Semiempirical Calculation of [60]Fullerenes Attached with Piperidinodithiocarboxylate and 7-Chloro-phenazine

[60]Fullerenes attached with piperidinodithiocarboxylate dyad （1） and 7-chloro-1,2,3,4-tetrahydrophenazine （2） were efficiently synthesized through Diels-Atder cycloaddition with dienes. The physical properties of the triplet states of these compounds, in which strong electron acceptor moieties were covalently attached to C60 cores, were investigated by nanosecond laser flash photolysis. The excited triplet states in benzonitrite have been evaluated by observing the transient absorption bands in the near-IR region. The HOMO and LUMO were calculated by semiempirical methods AM1, which could predict the intramolecular photoinduced electron transfer in 1 and 2, and the nanosecond transient absorption spectra observed experimentally in solution were in excellent agreement with the calculated ones.     

Photophysical Properties and Photoinduced Electron Transfer between[60]Fullerene—containing Cyclic Sulphoxide [C60—C60H8SO]and Tetrathiafulvalene（TTF） by Laser Flash Photolysis

Photoinduced electron transfer(PET) processes between C60-C6H8SO and Tetrathiafulvalene(TTF) have been studied by nanosecond laser photolysis.Quantrm yiekds(φet) and rate constants of electron transfer(ket) from TTF to excited triplet state of[60] fullerene-containing cyclic sulphoxide in benzonitrile(BN) have been evaluated by observing the transient absorption bands in the NIR region.With the decay of excited triplet state of [60]fullerene-containing cyclic suplhoxide,the rise of radical anion of [60]fullerene-containing cyclic sulphoxinde is observed.     

Synthesis of Fullerene-Acrylamide Copolymer Nanoball and Its Lubrication Properties

A novel fuUerene-acrylamide copolymer was synthesized via radical polymerization. It is soluble in polar solvents such as water, dimethyl sulfoxide etc. The product was characterized by FTIR, UV-Vis and GPC. TEM analysis shows that the average particle diameter is about 46 nm. Four-ball tests show that the addition of a certain concentration of the fullerene copolymer to base stock (2 wt% triethanolamine and 0.5 wt% OPZ aqueous solution) can effectively raise the load-carrying capacity (PB value) and the antiwear ability. SEM analysis shows that the addition results in reducing diameter of wear scar and decreasing wear.     

Aggregation Properties of an Amphiphilic Methanofullerene Derivative in THF-H20 Solvent Mixtures

Amphiphilic methanofullerene 1 exhibits strong tendency to form aggregates in THF-H20 solvent mixtures. Two different aggregation processes induced by either varying the solvent composition or upon standing have been found. Concentration has great influence on the aggregation process. Paralleling to the UV-Vis changes, an unusual solvatochromism has been observed in these two different processes.     

[2＋2] Photocycloaddition of [60] Fullerene with Podophyllotoxin Derivative Containing Cyclohexadienone Group

Photochemical [2 2] cycloaddition of C60 with podophyllotoxin derivative containing a cyclohexadienone group in o-dichlorobenzene afforded an isomeric mixture of adducts and a pure adduct of C60-fused podophyllotoxin derivatives. The structures of the products were characterized by MS, NMR and IR spectra.     

Efficient and Convenient Preparation of Water-Soluble Fullerenol

An efficient and convenient preparation of fullerenols was described. With polyethylene glycol (PEG) 400 as catalyst, fullerenols were conveniently synthesized via the direct reaction of fullerene with aqueous NaOH. By control of reaction conditions, either water-soluble C60 fullerenol or water-insoluble C60 fullerenol could be obtained selectively.     

Solvent-free Synthesis of Dihydrofuran-fused [60]Fullerene Derivatives by High-speed Vibration Milling

Solvent-free organic reactions have been attracting great interest of chemists due to the elimination of the usage of harmful organic solvents,low costs,and simplicity in the procedure1.Solvent-free mechanochemical reactions of fullerenes were explored and are significant for the reactions of fullerenes because the low solubility of fullerenes in common organic solvents requires large quantity of organic solvents and some novel fullerene reactions could only occur in the solid-state reaction2.…     

Solvent-free Mechanochemical and Liquid-phase Reaction of [60]Fullerene with Ethyl 2-Diazopropionate

The solvent-free mechanochemical reaction and the liquid-phase reaction of C60 with ethyl 2-diazopropionate prepared in situ or preformed from alanine ethyl ester hydrochloride and sodium nitrite have been investigated. Methanofullerene 1 and fulleroids 2 and 3 from these reactions were obtained, meanwhile the pyrazoline intermediate was not observed. Fulleroids 2 and 3 can be converted to methanofullerene 1 in refluxing toluene.     

Synthesis of a Novel Organic Soluble and Thermal-stable Fullerene-perylene Dyad

A novel organic soluble and thermal-stable fullerene-perylene dyad, in which a perylenemoietyis attached to C60, has been prepared by 1, 3-dipolar cycloaddition of the azomethine ylidesgenerated in situ from the aldehyde and N-methylglycine and characterized by NMR, FT-IR, TGA,absorption and fluorescent spectra etc.     

Photophysical Properties and Photoinduced Electron Transfer between [60] Fullerene-Containing Cyclic Sulphoxide [C_(60)-C_6H_8SO] and Tetrathiafulvalene (TTF) by Laser Flash Photolysis

ＩｎｔｒｏｄｕｃｔｉｏｎＥｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｃｈｅｍｉｓｔｒｙｈａｓｂｅｅｎａｔｏｐｉｃｓｉｎｔｅｎ ｓｉｖｅｌｙｓｔｕｄｉｅｄｉｎｂｉｏｌｏｇｉｃａｌａｎｄａｒｔｉｆｉｃｉａｌｓｙｓｔｅｍｓ .[6 0 ]Ｆｕｌｌｅｒｅｎｅ ｃｏｎｔａｉｎｉｎｇｅｌｅｃｔｒｏａｃｔｉｖｅｄｏｎｏｒ ａｃｃｅｐｔｏｒｄｙａｄｓｈａｖｅｂｅｃｏｍｅｃｕｒｒｅｎｔｆｏｃｕｓｏｆｒｅｓｅａｒｃｈｉｎｔｈｅｆｉｅｌｄｏｆｅｆｆｉｃｉｅｎｔｃｏｎｖｅｒｓｉｏｎｏｆｓｏｌａｒｅｎｅｒｇｙｔｏｕｓａｂｌｅｆｏｒｍｓｏｆｅｎ…     

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识. 本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱. 结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程. 结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种. 本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向.     

Kinetics and Energetics of Intramolecular Electron Transfer in Single-Point Labeled TUPS-Cytochrome c Derivatives

Electron transfer within and between proteins is a fundamental biological phenomenon, in which efficiency depends on several physical parameters. We have engineered a number of horse heart cytochrome c single-point mutants with cysteine substitutions at various positions of the protein surface. To these cysteines, as well as to several native lysine side chains, the photoinduced redox label 8-thiouredopyrene-1,3,6-trisulfonate (TUPS) was covalently attached. The long-lived, low potential triplet excited state of TUPS, generated with high quantum efficiency, serves as an electron donor to the oxidized heme c. The rates of the forward (from the label to the heme) and the reverse (from the reduced heme back to the oxidized label) electron transfer reactions were obtained from multichannel and single wavelength flash photolysis absorption kinetic experiments. The electronic coupling term and the reorganization energy for electron transfer in this system were estimated from temperature-dependent experiments and compared with calculated parameters using the crystal and the solution NMR structure of the protein. These results together with the observation of multiexponential kinetics strongly support earlier conclusions that the flexible arm connecting TUPS to the protein allows several shortcut routes for the electron involving through space jumps between the label and the protein surface.     

单加成环丙烷富勒烯膦酸酯衍生物的合成与电化学性能

在Mn(OAc)₃•2H₂O催化下, C₆₀分别和亚甲基二膦酸四乙酯、氰基亚甲基膦酸二乙酯或乙氧羰基亚甲基膦酸二乙酯在氯苯中回流, 生成3个单加成环丙烷富勒烯膦酸衍生物C₆₀C(R)PO(OEt)₂ [1, R＝PO(OEt)₂; 2, R＝COOEt; 3, R＝CN]. 与以前报道的Bingel反应法相比, 该方法副产物少并且缩短了反应时间. 采用循环伏安法发现1, 2的还原电位相对于C₆₀发生负移, 而3的还原电位相对于C₆₀却正移40 mV, 表明引入象氰基一样具有很强吸电子能力的取代基团, 可以改善富勒烯球的电化学性能, 合成电子接受能力较强的富勒烯衍生物.     

苯醚键相联的C_(60)-卟啉二元化合物的合成、电化学和光谱性质研究(英文)

设计合成了一系列苯醚键相连的C60-卟啉二元化合物及其金属锌配合物:H2Por-p-C60、H2Por-m-C60、H2Por-o-C60、ZnPor-p-C60、ZnPor-m-C60和ZnPor-o-C60,通过质谱、元素分析和核磁共振氢谱对它们的结构进行了表征。基态的电子吸收光谱和电化学研究表明在这些二元体系中C60和卟啉之间存在明显的相互作用。荧光光谱研究表明卟啉单元的荧光几乎被C60单元完全淬灭,并且它们之间的连接位置对荧光淬灭的效率具有显著影响。     

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.     

Excited‐State Dynamics of the Metal String Complex Co3(dpa)4(NCS)2 from Femtosecond Transient Absorption Spectra

Transient absorption spectroscopy is used to study the excited‐state dynamics of Co₃(dpa)₄(NCS)₂, where dpa is the ligand di(2‐pyridyl)amido. The ππ*, charge‐transfer, and d–d transition states are excited upon irradiation at wavelengths of 330, 400 and 600 nm, respectively. Similar transient spectra are observed under the experimental temporal resolution and the transient species show weak absorption. We thus propose that a low‐lying metal‐centered d–d state is accessed immediately after excitation. Analyses of the experimental kinetic traces reveal rapid conversion from the ligand‐centered ππ* and the charge‐transfer states to this metal‐centered d‐d state within 100 fs. The excited molecule then crosses to a second d–d state within the ligand‐field manifold, with a time coefficient of 0.6–1.4 ps. Because the ground‐state bleaching band recovers with a time coefficient of 10–23 ps, we propose that an excited molecule crosses from the low‐lying d–d state either directly within the same spin system or with spin crossing via the state ²B to the ground state ²A₂ (symmetry group C₄). In this trimetal string complex, relaxation to the ground electronic surface after excitation is thus rapid.     

[60]富勒烯的化学修饰及其功能材料性能研究

本文总结了近十几年的文献资料，对[60]富勒烯的化学修饰及其功能材料性能研究进行综述。     

C60富勒烯-哌啶硫代荒酸酯稠合体的合成与三线态特征

C₆₀富勒烯与2-(哌啶-硫代荒酸酯)-1,3-丁二烯通过Diels-Alder环加成反应得到C₆₀富勒烯-哌啶硫代荒酸酯稠合体,运用现代波谱技术等确定了产物结构;用半经验方法PM3和AM1计算预测环加成反应性和C₆₀富勒烯-哌啶硫代荒酸酯稠合体的性能.激光光解时间分辨技术初步探究了单加成的C₆₀富勒烯-哌啶硫代荒酸酯稠合体(C₆₀-PX)三线态特征以及与四-(2-噻吩基)-四硫富瓦烯(TT-TTF)分子间的光诱导电子转移反应.