反,反-1,4-双[β-(4-取代苯基)乙烯基]苯衍生物紫外光谱的溶剂效应

测定了某些反,反-1,4-双[β-(4-取代苯基)乙烯基]苯衍生物在17种溶剂及不同比例的非极性混合溶剂中的紫外光谱,一般,最大吸收峰位置随溶剂的折光系数增大而红移,同时,在极性、非极性及不同比例非极性混合溶剂中紫外光谱的_(max)值与(n~2-1)/(2n~2+1)之间呈线性关系。     

水溶性1，8-萘酰亚胺衍生物的合成及其对有机溶剂中少量水的识别

萘二甲酸酐与2-(2-氨乙基氨基)乙醇在乙醇中反应合成了一种新型水溶性1,8-萘酰亚胺衍生物--N-[2-(2-羟乙基氨基)-乙基]-1,8-萘酰亚胺(3),其结构经1H NMR,IR,MS和元素分析表征.荧光光谱分析发现3在不同溶剂中具有不同的荧光性质,在非(或弱)极性-非质子性溶剂、极性-非质子溶剂中几乎不产生或产生较弱的荧光,而在极性-质子性溶剂中产生较强的荧光,在水中的荧光最强.这种特性使3有望用于识别有机溶剂中的少量水.     

醋酸锰作用下二烯丙基叔胺与[60]富勒烯的自由基环加成反应

二烯丙基叔胺与[60]富勒烯在醋酸锰作用下发生自由基环加成反应,生成[60]富勒烯并吡咯烷衍生物.醋酸锰的用量和反应温度等因素对反应有一定影响.反应可能先由Mn(Ⅲ)与烯丙胺经单电子氧化产生自由基,再与[60]富勒烯加成并进一步环化.研究中得到的各产物的结构均通过波谱学方法表征.     

4,4′-二胺甲基联苯搭桥的二苯并-18-冠-6环状二聚体的合成

在高度稀释条件下 ,二酰氯 (1)与二氨基二苯并 18 冠 6 (2 )反应 ,以高收率生成大环二酰胺 (3) ,3在甲苯溶剂中用SMEAH[二 (2 甲氧乙氧基 )二氢化钠铝 ]还原得到目标化合物——— 4,4′ 二胺甲基联苯搭桥的二苯并 18 冠 6环状二聚体 (4 ) .在吡啶溶剂中 4与 [6 0 ]富勒烯有弱的π 电子给体 -受体相互作用 .     

1,3-二β-萘甲酰基杯[4]芳烃的荧光光谱与光二聚反应

本文合成了含荧光发色团的杯芳烃衍生物1,3-二β-萘甲基杯[4]芳烃1,研究了它在极性溶剂及非极性溶剂中的光物理与光化学行为,并通过萘发色团荧光及光二聚反应研究了杯[4]芳烃衍生物的构象。     

1-(4-叔丁基苯基)-1,1-二[4-(4-硝基苯氧基)\]苯基乙烷的合成及其溶解性研究

以叔丁基苯为起始原料,经3步反应制得了一种新化合物1-(4-叔丁基苯基)-1,1-二[4-(4-硝基苯氧基)]苯基乙烷（3）,总收率61.14%,其结构经¹H NMR和IR表征。3可溶于非极性溶剂（石油醚除外）和极性非质子溶剂。     

[60]富勒烯衍生物的对称性、碳笼结构与13C NMR谱

本文全面综述了多种[60]富勒烯衍生物的结构,阐述了(13)~C NMR谱在[60]富勒烯衍生物结构表征中的应用,重点讨论了不同对称性[60]富勒烯衍生物的(13)~C NMR谱图特征.通过[60]富勒烯部分(13)~C共振线的化学位移、数目和相对强度,可以确定[60]富勒烯衍生物的对称结构和加成方式.对于C_s、C_(2v)和C_(3v)对称性的[60]富勒烯衍生物,镜面上的碳原子的相对化学位移很大程度上取决于他们距加成位置的距离.因此,(13)~C NMR谱在碳笼具体结构的确定中具有不可替代的作用.     

C60-苯乙烯-顺丁烯二酸酐的三元自由基共聚

自从研制出克量的Ｃ6 0 [1],其在超导光、电、磁、生物等领域的研究迅速发展 .由于Ｃ6 0 只溶于几种非极性溶剂中 ,其使用受到限制 ,从而制备Ｃ6 0 的高分子衍生物一直被认为是Ｃ6 0 材料化的重要途径[2 6 ].文献 [39]报道 ,富勒烯与含双键的单体如苯乙烯、甲基丙烯酸甲酯等可很方便地进行自由基共聚 ,得到富勒烯与烯类单体的共聚物 ,产物可溶于四氢呋喃等有机溶剂 .但迄今为止 ,可溶于水或其它强极性溶剂中的Ｃ6 0 聚合物研究的很少[10 ,11],而Ｃ6 0 的三元共聚物的制备几乎未见报道 ,为此 ,我们采用自由基共聚制备了Ｃ6 0 苯乙烯 顺丁烯…     

[60]富勒烯衍生物的对称性、碳笼结构与C NMR谱

本文全面综述了多种[60]富勒烯衍生物的结构,阐述了(13)~C NMR谱在[60]富勒烯衍生物结构表征中的应用,重点讨论了不同对称性[60]富勒烯衍生物的(13)~C NMR谱图特征.通过[60]富勒烯部分(13)~C共振线的化学位移、数目和相对强度,可以确定[60]富勒烯衍生物的对称结构和加成方式.对于C_s、C_(2v)和C_(3v)对称性的[60]富勒烯衍生物,镜面上的碳原子的相对化学位移很大程度上取决于他们距加成位置的距离.因此,(13)~C NMR谱在碳笼具体结构的确定中具有不可替代的作用.     

4，4′－二胺甲基联苯搭桥的二苯并－18－冠－6环状二聚体的合成

在高度稀释条件下，二酰氯（1）与二氨基二苯并－18－冠－6（2）反应，以 高收率生成大环二酰胺（3），3在甲苯溶剂中用SMEAH[二（2－甲氧乙氧基）二氢 化钠铝]还原得到目标化合和-4,4′－二胺甲基联苯搭桥的二苯并－18－冠－6环状 二聚体（4）。在吡啶溶剂中4与[60]富勒烯有弱的π－电子给体－受体相互作用。     

Absorption spectrophotometric study of supramolecular complexation of [60]- and [70]fullerenes with 24,26-dimethoxy-25,27-dihydroxy calix[4]arene

Supramolecular interactions of 24,26-dimethoxy-25,27-dihydroxy calix[4]arene (1) with [60]- and [70]fullerenes have been studied in only chloroform and in a ternary solvent mixture comprising of chloroform, ethyl alcohol and toluene by UV-vis absorption spectrophotometric method. The experimental results are explained using the model that takes into account the interaction between electronic subsystems of 1 and fullerene. The most interesting feature is the preference of [60]fullerene over [70]fullerene for 1 in ternary solvent mixture as revealed by higher value of formation constant of [60]fullerene/1 complex. The selectivity towards [60]fullerene opens up the way toward self-assembling systems and new separation and purification methods for fullerenes.     

Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

Cyclic voltammetry (CV) measurements on (eta(2)-C(60))M(CO)(5) complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E(1/2) values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn-Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene-metal pi-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (eta(2)-C(60))M(CO)(5) complexes. Analysis of the activation parameters for the metal-[60]fullerene dissociation, the metal-[60]fullerene bond enthalpies (from DFT computations), and metal-solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent-M(CO)(5). Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.     

Addition of diphenylphosphinoyl azide to [60]fullerene

The reaction of [60]fullerene with diphenylphosphinoyl azide in toluene or ino-dichlorobenzene in the presence of traces of water affords 2-[N-(diphenylphosphoryl)amino]-1-hydroxy[60]fullerene This reaction in THF gives a mixture of (N-diphenylphosphoryl)[60]fullerenol[1,2-b]aziridine and a product of partial hydrolysis of the bisadduct of phosphorylated azide and fullerene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2168–2172, November, 1999.     

Synthesis and photoinduced energy- and electron-transfer processes of C60-oligothienylenevinylene-C70 dumbbell compounds

Unsymmetric dumbbell molecules based on N-methylpyrrolidine[60]fullerene, oligothienylenevinylenes (nTV; n=2, 4), and N-methylpyrrolidine[70]fullerene, namely, C(60) -nTV-C(70) were synthesized and their photophysical properties were studied. In nonpolar solvents, photoinduced energy-transfer process predominantly takes place from the singlet excited state of nTV to C(60) and C(70) , as was confirmed by time-resolved emission and transient absorption spectroscopy. In polar solvent, charge-separation processes take place instead of energy transfer. The generated charge-separated radical-ion pairs decay to the neutral molecules by a fast charge-recombination process; for n=4, a rate constant of 2×10(7) s(-1) and lifetime of 50 ns were evaluated.     

Dimeric capsules with a nanoscale cavity for [60]fullerene encapsulation

The acid-assisted and guest-induced formation of superstructures was achieved by the addition of haloacetic acids to a toluene solution of the resorcin[4]arene derivatives 1 and [60]fullerenes. The formation of dimeric superstructures that encapsulated a nanosized guest molecule was observed when appropriate acids, such as haloacetic acids, and suitable guest molecules, such as [60]fullerenes, were co-added to a toluene solution of cavitand 1 that has four pyridine units, whereas a complicated equilibrium between several species was detected without [60]fullerenes, and the formation of discrete superstructures was not monitored in the absence of haloacetic acids. The spectroscopic data indicate that the formed [60]fullerene-encapsulated complexes have the structure of 2. These complexes are self-assembled through pyridinium-anion-pyridinium interactions and by pi-pi and van der Waals interactions. The rate of decomplexation of 2 is estimated to be 3.1 s(-1) from a 2D exchange NMR spectrum. The [60]fullerene encapsulation process can be controlled by modifying the amounts of acids used, changing the temperature of the system, altering the ratio of acid/base, and even through varying the solvent polarity. Moreover, the fluorescence spectra show band-narrowing spectral changes and a retardation of the relaxation characteristics of isolated and isotropic [60]fullerenes, which indicates that the environmental change around [60]fullerene is induced upon its encapsulation.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

以C_(70)衍生物为电子受体的高效聚合物固体薄膜太阳能电池

以PC[70]BM(phenyl C71-butyric acid methyl ester)取代PC[60]BM(phenyl C61-butyric acid methyl ester)作为电子受体材料,以MEH-PPV(poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene])为电子给体材料,制成了本体异质结(bulk heterojunction,BHJ)聚合物太阳能电池.MEH-PPV/PC[70]BM器件在AM1.5G(80 mW/cm2)模拟太阳光的光照条件下得到了3.42%的能量转换效率,短路电流值达到了6.07 mA/cm2,开路电压0.85 V,填充因子为53%.通过紫外可见吸收光谱和外量子效率的研究,发现PC[70]BM作为电子受体,对扩大光谱的吸收范围和增加活性层的吸收系数有明显的作用.同时比较了不同溶剂对该体系器件性能的影响.通过原子力显微镜(AFM)、光暗导I-V曲线等研究,分析了1,2-二氯苯有利于给体相和受体相的微相分离和载流子的传输的原因.     

Efficient preparation of monoadducts of [60] fullerene and anthracenes by solution chemistry and their thermolytic decomposition in the solid state

The efficient preparation of monoadducts of [60]fullerene and seven anthracenes (anthracene, 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 2,3,6,7-tetramethylanthracene, and 2,6-di-tert-butylanthracene) by cycloaddition in solution is described. The seven mono-adducts of [60]fullerene and the anthracenes were characterized spectroscopically and were obtained in good yields as crystalline solids. The monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 2-methylanthracene and 9,10-dimethylanthracene crystallized directly from the reaction mixture. The thermolytic decomposition at 180 degrees C of the crystalline monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 9-methylanthracene and 9,10-dimethylanthracene all gave rise to the specific formation of a roughly 1:1 mixture of [60]fullerene and the corresponding antipodal bisadducts ("trans-1"-bisadducts) of [60]fullerene and the anthracenes. In contrast, the crystalline monoadducts of [60]fullerene and the anthracene derivatives 2-methylanthracene, 2,3,6,7-tetramethylanthracene and 2,6-di-tert-butylanthracene all decomposed to [60]fullerene and anthracenes (without detectable formation of bisadducts) upon heating in the solid state to temperatures of 180 to 240 degrees C. The formation of the antipodal bisadducts from thermolytic decomposition of crystalline samples of the monoadducts was rationalized by topochemical control.     

A comparative study of molecular complexation of [60]- and [70]fullerenes with 1,3,5-tribromobenzene by UV-vis spectrophotometric method

By UV-vis spectrophotometric method it has been shown that 1,3,5-tribromobenzene (TBB) forms molecular complexes of 1:2 stoichiometry with [60]- and [70]fullerenes. An isosbestic point could be detected in case of the [70]fullerene complex. The formation constant of the [60]fullerene complex is higher than that of the [70]fullerene complex at each of the four temperatures under study. This is in opposite order of the electron affinities of the two fullerenes; moreover, no charge transfer band was observed in the spectra of either complex in solution. This indicates that van der Waals forces, rather than CT interactions, are responsible for complexation. The results reveal that the C-atoms at the pentagon vertices of [60]fullerene have greater polarizing power than those in [70]fullerene.     

Solution NMR studies of supramolecular complexes of [60]- and [70]fullerenes with mono O-substituted calix[6]arene

Supramolecular complexation of [60]- and [70]fullerenes with 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert butyl)calix[6]arene (I) has been studied in CCl(4) medium by NMR spectrometric method. All of the complexes are found to be stable with 1:1 stoichiometry. Formation constants (K) of the above supramolecular complexes have been determined from systematic variation of NMR chemical shifts of specific protons of I in the presence of [60]- and [70]fullerenes. Trends in the K value suggest that [70]fullerene binds more strongly with I relative to [60]fullerene. Both PM3 and ab initio calculations reveal that the intermolecular interaction in the [70]fullerene/I complex proceeds through quite deep energy minima.