C~6~0与偶氮二异丁腈基自由基反应的ESR研究

C~6~0与偶氮二异丁基腈热分解产生的游离基(CH~3)~2CCN发生加成反应, 产物的红外光谱出现C~6~0和CN, CH的特征振动峰, ESR谱出现一对弱的肩峰, 中间的主峰容易功率饱和, 表明有两类物种存在, 提出了可能的反应机理。     

量子化学从头计算法研究C~7~6的分子静电势

在MNDO-PM3方法优化的分子结构基础上, 用Hartree-Fock/6-31G从头计算法研究了D2点群手性C~7~6稳定结构的分子静电势, 获得了过C~7~6对称中心的三个正交平面XY, XZ和YZ上的平面静电势图和径向静电势图, 并与C~6~0和C~7~0做了对比分析。     

不同有机溶剂中C~6~0溶解度与温度的关系

本文测定了温度280K以上C~6~0在一些有机溶剂中的溶解度与温度的依赖关系,发出280K以上C~6~0在正己烷、甲苯、二甲苯中溶解度随温度上升而减小, 表现出放热的溶解过程。与此相反, 在环己烷中C~6~0的溶解度却有所不同, 随着温度的升高而增大, 表现出吸热的溶解过程。     

钌铁双核配合物的合成及猝灭[Ru(bpy)~3]^2^+发光过程研究

合成了含二氮芴和联吡啶等配体的一系列新型钌铁双核配合物:[(C~1~0H~6N~2)C=N-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,[(C~1~0H~6N~2)C=N--C~6H~4-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,[(C~1~0H~6N~2)C=N-C~6H~4-C~6H~4-N=CR-Fc)Ru(bpy)~2]·(PF~6)~2,并对其进行了光谱表征,通过对该类配合物的循环伏安和发光光谱研究,讨论其激发态的氧化还原性和对[Ru(bpy)~3]^2^+发光过程的猝灭作用.研究表明猝灭过程为扩散控制的双分子交换能量传递     

富勒烯(C~6~0, C~7~0)的金属有机化学

综述了1990年以来富勒烯金属有机化学研究的进展,结果表明富勒烯(C~6~0,C~7~0)能与第VIII及IVB、VB、VIB、VIIB族等过渡金属形成各类衍生物,具有潜在的应用前景。     

富勒烯C~6~0与二茂铁酮亚胺电荷转移相互作用的研究

C~6~0与三种二茂铁酮亚胺η^5-C~5H~5Fe[C~5H~4C(CH~3)=N-C~6H~4R-p]-η^5(1a R=H,1bR=CH~3,1c R=OCH~3)在甲苯和室温下可发生电荷转移相互作用形成三种电荷转移配合物η^5-C~5H~5Fe[C~5H~4C(CH~3)=N-C~6H~4R-p]-η^5/C~6~0 (2a R=H,2b R=CH~3,2c R=OCH~3)。通过紫外光谱证实了它们的存在,并用Benesi-Hildebrand方程求出了2a、2b和2c的电荷转移平衡常数分别为0.769、0.928和2.353mol^-^1·dm^3。鉴于它们远大于普通有机胺与C~6~0形成的电荷转移配合物的平衡常数,因此可认为在2a～2c中存在着由二茂铁核及亚胺基向C~6~0的双重电荷转移相互作用。     

C~6~0O异构体的研究

本文用臭氧氧化C~6~0的苯溶液,用HPLC分析产物,室温下氧化产物只得到一个C~6~0O异构体组分峰。低温下产物得到两个C~6~0O异构体组分峰。多出的一个峰经实验与理论的研究,表明它很可能是异构体C~6~0O(C~s)。     

C~6~0^2^-单态和三态的结构和光谱性质

用INDO系列方法对C~6~0^2^-单态和三态分别进行了几何构型优化, 得到D~2~h对称性的构型, 表明C~6~0^2^-确实发生了Jahn-Teller畸变, 导致双键变长, 形成15种键, 9种不等同碳原子, 其额外负电荷主要分布在赤道附近, 以此构型为基础,计算了C~6~0^2^-的电子光谱, 与实验值基本一致, 对光谱进行了理论指认, 说明了光谱红移的原因。     

C~6~0乙醇胺铂配合物的合成及其催化硅氢化性能

C~6~0与乙醇胺反应,然后与亚氯铂酸钾络合,制得了含配位氮原子的富勒烯铂配合物。该配合物能有效地催化烯烃与三乙氧基硅烷的硅氢化反应,并对苯乙烯有独特的催化性能,以近100%的区域选择性得到α-加成产物。还对催化机理进行了初步的探讨。     

C~6~0^3^-的Jahn-Teller变形、电子结构和光谱性质的理论研究

本文用INDO系列方法对C~6~0^3^-进行了几何构型优化, 得到D~2~h构型, 表明C~6~0^3^-确实发生了Jahn-Teller变形, 导致单键变短, 双键变长, 其额外负电荷和单电子主要分布在赤道附近。以此构型为基础, 计算其电子吸收光谱, 与实验值基本吻合, 在对光谱进行理论指认的同时, 讨论了光谱红移的原因。     

基于富勒烯衍生物修饰玻碳电极的DNA电化学传感器

以富勒烯C₆₀, L-苏氨酸及对苯二甲醛为原料, 在氮气保护下反应得到含醛基官能团的2-(4-醛基苯基)-5-(1-羟乙基)富勒烯吡咯烷衍生物(C₆₀-CHO). 将该材料修饰于玻碳电极表面, 并利用醛基与氨基之间温和、高效的缩合反应, 将5-氨基修饰的寡聚核苷酸共价固定到了C₆₀-CHO修饰的玻碳电极表面, 构建了一种新型的电化学DNA传感器. 以[Fe(CN)₆]^3−/4−为电活性探针, 采用电化学阻抗法对转基因植物CaMV35S启动子基因特征片段进行检测. 实验结果表明, 杂交前后的电子传递电阻差值(DR_et)与目标序列浓度对数(lg C_S2)在1.0×10^－13～1.0×10^－9 mol/L浓度范围内呈良好的线性关系, 线性回归方程为DR_et/(10³ Ω)＝3.471 lg (C_S2/mol/L)＋50.425 (r＝0.9977), 检测限为1.5×10⁻¹⁴ mol/L. 杂交特异性实验进一步表明该传感器对完全互补、碱基错配和非互补序列具有良好的识别能力.     

液液界面反应制备C60微米管阵列及其上转换荧光性能研究

采用C60/甲苯溶液和异丙醇作为原料,通过液液界面渗透反应在AAO模板上制备了垂直定向排列的C60微米管阵列.通过SEM、XRD、Raman、荧光光谱(PL)对材料的结构和性能进行测试表征.结果表明C60微米碳管阵列由C60分子聚合而成,为面心立方结构,微米管直径5～10 μm、壁厚1～3 μm.在1064 nm近红外入射光激发下样品在红光区域发生了上转换发光,分析表明这是由多壁碳管丰富的能级所造成.     

Absorption spectrophotometric, fluorescence, transient absorption and quantum chemical investigations on fullerene/phthalocyanine supramolecular complexes

The present paper reports the photophysical investigations on supramolecular interaction of a phthalocyanine derivative, namely, 2,9,16,23-tetra-tert-butyl-29H,31H-Pc (1) with C(60) and C(70) in toluene. The binding constants of the C(60) and C(70) complexes of 1 are estimated to be 27,360 and 25,205 dm(3), respectively. Transient absorption measurements in the visible region establishes that energy transfer from C60*T (and C70*T) to 1 occurs predominantly in toluene which is subsequently confirmed by the consecutive appearance of the triplet states of 1. Quantum chemical calculations at DFT level of theory explore the geometry and electronic structure of the supramolecules and testify the significant redistribution of charge between fullerenes and 1.     

C3v-symmetrical tribenzotriquinacenes as hosts for C60 and C70 in solution and in the solid state

Various tribenzotriquinacenes (TBTQs), most of which incorporate six functional groups at the periphery of their C3v-symmetrical, rigid and convex-concave molecular framework, have been studied with respect to their ability to form supramolecular complexes with the C60 and C70 fullerenes, either in the solid state or in solution. The hexabromo derivative Br6-TBTQ was cocrystallized with C60 as [Br6-TBTQ相似文献   

The reaction of fullerene C(60) with 4,6-dimethyl-1,2,3-triazine: formation of an open-cage fullerene derivative.

A thermal reaction of fullerene C(60) with 4,6-dimethyl-1,2,3-triazine (4) in o-dichlorobenzene gave azacyclohexadiene-fused fullerene derivative 5, by the reaction with intermediate azete 11, and then, after flash chromatography over SiO(2), open-cage fullerene derivative 6 having an eight-membered ring orifice on the C(60) cage. Compound 6 is assumed to be formed via addition of diradical intermediate 13 to C(60). Compound 6 underwent a further photochemical reaction with singlet oxygen with the cleavage of one of the double bonds at the rim of the orifice to afford triketone derivative 8 having a 12-membered ring orifice.     

甲苯/水双相体系中以稻草为原料合成糠醛

FeCl³为催化剂,在甲苯/水双相溶剂体系中,以稻草为原料经水解反应制备糠醛,其结构经¹H NMR和¹³C NMR确证。通过响应面分析获得的最佳反应条件为：催化剂质量分数23.09%,甲苯60 mL,溶剂比V（甲苯）: V（水）=1 : 1,料液比为67.5 g·L^-1,于177 ℃反应60 min,糠醛收率高达78.92%。     

气相C60与甲苯,氯化苄和对二甲苯反应研究

在质谱离子源内,气相C_(60)分别与甲苯、氯化苄、对二甲苯产生的主要碎片离子及自由基反应,生成了C_(60)的多种气相衍生物离子,表明气相下C_(60)具有很活泼的化学性质。     

The reaction of fullerene C(60) with phthalazine: the mechanochemical solid-state reaction yielding a new C(60) dimer versus the liquid-phase reaction affording an open-cage fullerene.

The reaction of fullerene C(60) with phthalazine was studied both in solution and in the solid state using the high-speed vibration-milling technique. The reaction in solution gave open-cage fullerene derivative 1 in 44% yield by a one-pot reaction. In contrast, the solid-state reaction afforded dimeric derivative 2 as the sole product. Dimeric derivative 2 was found to undergo intramolecular [2 + 2] cycloaddtion between the two C(60) cages located in close proximity to give a new C(60) dimer 6 in quantitative yield. The structures of these new derivatives of C(60) were determined by spectroscopic methods, and the electrochemical behavior of 2 and 6 was also studied.     

C_（60）的胺加成反应和电喷雾电离质谱（ESI－MS）检测

报道了Ｃ６０与１，３－丙二胺和Ｎ，Ｎ－二甲基－１，３－丙二胺的加合反应，反应产物未经预先离子化处理直接用ＥＳＬ－ＭＳ进行检测。由于反应产物从甲苯溶液中析出，避免了生成多胺基加合物，产物以单加成物为主。当加合反应在空气氛下进行时，有加合氧的产物Ｃ６０Ｏｎ（ＮＨ２—ＣＨ２ＣＨ２ＣＨ２ＮＲ２）ｍ（Ｒ＝Ｈ，ＣＨ３）存在。实验发现：Ｎ，Ｎ－二甲基－１，３－丙二胺比１，３－丙二胺更容易与Ｃ６０发生多胺基加成和氧加成反应。通过控制反应条件可制备Ｃ６０二胺的单加成产物。     

Synthesis and photophysical characteristics of 2,7-fluorenevinylene-based trimers and their electroluminescence

Three new 2,7-fluorenevinylene-based trimers were synthesized and characterized. The synthesis was carried out by the Heck coupling reaction of 9,9-dihexyl-2,7-divinylfluorene with 2-(4-bromophenyl)-5-phenyl-1,3,4-oxadiazole, N,N-diphenyl-4-bromoaniline, or 3-bromopyrene to afford the trimers OXD, TPA, and PYR, respectively. All the trimers were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. Their glass transition temperatures ranged from 33 to 60 degrees C. The UV-vis spectra showed an absorption maximum at lambda(a,max) = 379-417 nm with optical band gap of Eg = 2.47-2.66 eV. In solution, they emitted strong blue-green photoluminescence (PL) with PL maximum at lambda(f,max) = 455-565 nm and fluorescence quantum yield of Phi(f) = 0.65-0.74. On the other hand, in their spin-coated films, the PL efficiencies significantly decreased due to the presence of concentration quenching. All samples showed nanosecond transient lifetime containing two components, suggesting excimer formation. The organic light-emitting diodes (OLEDs) with OXD and TPA showed green emission with electroluminescence (EL) quantum efficiencies of eta(EL) approximately 10(-2)%, while very weak EL efficiency of eta(EL) approximately 10(-5)% was observed with PYR. The highest occupied molecular orbital (HOMO) levels of the films were found to be 5.05-5.75 eV.