若干全氟环烃及其衍生物的拉曼光谱

由于C—F键的强极性,其振动模式在红外光谱中表现为强吸收谱带,而在拉曼光谱中则较弱,因此早期关于有机氟化合物振动光谱的研究以红外光谱为多,这方面Brown和Morgan已有详细总结.但有机氟化物的某些骨架振动往往呈现强的拉曼谱带.近年来对环状有机物的拉曼光谱研究已有较全面的总结,但对全氟环烷类及其衍生物尚无较系统的研究.本文报道若干全氟环烃及其衍生物的拉曼光谱数据,讨论了环呼吸振动频率与环大小及取代基的关系,环内双键振动频率的特性.实验证明全氟环烃的某些光谱特征与碳氢的环烃有较大的差异.     

芴基张力半导体结构和光电性质的理论研究（英文）

通过对模型化合物环四-9,9'-二甲基-2,7-芴及其系列的环芴衍生物[n]CFs(n=3-8)的结构、张力能以及光电性质的研究来进一步探讨空间张力对材料光学及电学性质的影响。研究结果表明,随着化合物中芴基数量和直径的增加,张力能减小,能隙增大。具有相同芴基数目的环芴分子,随着分子中张力能减少,分子电离电势逐渐增加,而电子亲和能逐渐减小。通过对模型化合物的空穴和电子重整能研究发现,其数值很接近,说明该类材料是一类潜在的双极性传输材料。同时还发现[n]CFs中,随着张力的减少,其第二发射峰的波长发生了蓝移。综上所述,空间张力为设计多功能有机半导体材料提供了有力工具。     

单根(7,5)蛇形单壁碳纳米管的拉曼光谱(英文)

研究了单根(7,5)蛇形单壁碳纳米管的拉曼光谱特征,观察到了环呼吸振动峰(RBM)、环呼吸振动的倍频峰(2RBM)、介于中间频率的振动峰(IMF)、无规振动峰(D)、剪切振动峰(G)、中间频率振动峰(M)、剪切振动和环呼吸振动的和频峰(G+RBM)、面内横向光学声子和纵向声学声子的和频峰(iTOLA)、无规振动的二次共振峰(G′或者2D)以及其它一些归属不清楚的拉曼峰.不同激发波长和不同激发偏振拉曼光谱研究表明,这些拉曼光谱峰显示出了非常强的激发能量和激发偏振的选择性.     

紫外拉曼光谱研究FeAlPO_4-5分子筛的合成机理

利用紫外共振拉曼光谱和紫外-可见漫反射光谱对不同铁含量的 FeAlPO4-5 分子筛进行了研究. 结果表明, FeAlPO4-5 分子筛的骨架铁有 4 个特征的拉曼谱峰, 分别位于 630, 1060, 1140 和 1210 cm?1. 当凝胶中 Al/Fe 比小于 380 时, 只有一部分铁离子可以进入分子筛形成四配位的骨架铁物种; 而另一部分则以骨架外六配位的铁物种存在, 其特征拉曼谱峰位于 285 cm?1. 结合紫外拉曼光谱、紫外-可见漫反射光谱和 X 射线衍射研究了 Al/Fe 比为 760 时 FeAlPO4-5 分子筛的晶化过程. 结果发现, 在分子筛晶化前, 铁物种以六配位的形式存在, 它为分子筛前体中的一维链状磷酸铝添加了一个惰性端基, 六配位的 Fe-O 键不利于它与其它磷酸铝物种发生反应; 当分子筛开始晶化时, 带有铁离子端基的磷酸铝链与其它磷酸铝链进一步反应形成分子筛骨架. 同时, 六配位的铁离子和邻近的磷酸铝物种反应转化为四配位的骨架铁物种.     

取代基对咔咯锰(V)-氧配合物Mn―O的成键影响

用密度泛函理论(DFT)方法对一系列A₃型咔咯锰(V)氧配合物进行了理论计算. 结果表明: 咔咯锰(V)-氧配合物中Mn―O键是由1 个σ键和2 个π键构成的叁键结构; 当咔咯中位取代基由推电子过渡到拉电子性质时, 咔咯骨架紧缩, Mn―O键缩短, 其拉曼光谱的伸缩振动峰往高波数移动; 取代基与氧原子的静电作用模式由正-负吸引转化为负-负排斥, 导致Mn―O键解离能ΔE减少, 即拉电子基团有利于增强咔咯锰(V)-氧配合物氧原子的活泼性.     

侧链取代的芴苯共聚物的光电性质及其溶剂化效应研究

采用Suzuki偶联聚合的方法合成了一系列化学结构明确、侧基性质(长度、体积、给/吸电子性质)不同的Hairy-Rod型芴苯共聚物. 通过光谱、电化学和模拟计算等手段研究了苯环上不同性质的侧基取代芴苯聚合物的发光性质、电化学性质和溶剂化效应等, 同时研究了侧基性质的变化对这些物理性质的影响规律. 苯环上烷基侧链长度的改变对取代共聚物的光谱、电化学和发光效率等影响很小|而随着苯环上烷氧基侧链长度的增加, 聚合物的光谱稳定性逐渐增强, 荧光发射光谱中的0-1转变逐渐被抑制, 荧光发射半峰宽减小. 苯环上取代侧基的给/吸电子性质变化对聚合物的光电性能具有全面的影响, 改变取代侧基的给/吸电子性质可调节芴苯共聚物的发光颜色和HOMO, LUMO能级以及HOMO-LUMO能隙等, 因此, 通过引入不同性质的侧基可实现对此类聚合物光物理性能的调控. 溶剂的极性对聚合物溶液的光谱性质具有显著影响, 溶液光谱随溶剂极性的增大逐渐向长波移动. 当聚合物本身带有强极性基团时, 在强极性溶剂中将发生聚合物分子链与溶剂分子间的强极性相互作用, 从而会引起更复杂的结果.     

拉曼光谱在石墨烯结构表征中的应用

石墨烯是sp2碳原子紧密堆积形成的二维原子晶体结构,因其独特的结构与性质引起了科学家们的广泛关注.拉曼光谱是一种快速而又简洁的表征物质结构的方法.主要综述了拉曼光谱技术在石墨烯结构表征中应用的一些最新进展.首先,在系统分析石墨烯声子色散曲线的基础上介绍了石墨烯的典型拉曼特征(G'峰、G峰和D峰),讨论了G'峰、G峰和D峰在石墨烯层数的指认和石墨烯边缘与缺陷态分析中的应用;然后,通过对石墨烯拉曼G峰和G'峰的峰位、峰型以及强度的分析,讨论了石墨烯的层间堆垛方式、掺杂、基底、温度和应力等对石墨烯的电子能带结构的影响;最后,介绍了石墨烯中的二阶和频与倍频拉曼特征以及石墨烯的低频拉曼特征(剪切和层间呼吸振动模),并讨论了其对石墨烯结构的依赖性.     

镧系乙酰丙酮-α、β、γ、δ-四苯基卟啉络合物的红外和拉曼光谱

本文从测定11个稀土乙酰丙酮-α、β、γ、δ-四苯基卟啉络合物的红外和拉曼光谱中发现,由于四苯基卟啉与稀土离子络合,削弱了乙酰丙酮环上的M—O拉伸振动带,使此带向低波数位移,而且仍符合镧系的“四分组”和“斜W”效应,吡咯C—H摇摆振动～984cm~(-1)带亦基本符合此效应,络合物中PN—H拉伸振动带消失,出现M—N拉伸振动与卟啉环骨架振动等的复合振动带,因而上述的镧系变化规律消失.     

卟啉及BODIPY衍生物设计合成及光物理性质研究基于分子玻璃主体材料的极紫外(EUV)光刻胶研发

<正>第一部分卟啉及BODIPY衍生物设计合成及光物理性质研究大π共轭有机化合物因其优良光电性质近年来引起广泛关注.卟啉和BODIPY是两类具有特殊电子结构和光谱性质的共轭化合物,通过功能化修饰可以实现对其光电性质的调控。本论文工作针对基于卟啉和BODIPY结构的大π共轭化合物的合成和光物理性质开展研究工作。具体研究内容如下:1.设计合成了分别以咔唑、芴和芴酮为桥的β-β桥联环状锌卟啉化合物。共轭桥对卟啉环电子离域     

环状聚茚并茚及其取代衍生物电子结构和磁性研究

采用半经验的AM1法，对环状聚茚并茚及其取代物的电子结构进行了计算研究 ，探讨了其磁性和取代基效应．计算得到，环状聚茚并茚及其取代物皆表现半导体 性质且发现其中一种异构体可能具有磁性．取代基效应表明，吸电子基团的取代使 聚合物的电子亲合势增大，而给电子基团的取代则导致电离势减少，但取代基效应 不能改变聚合物的半导体性质．此外，无论吸电子基团还是给电子基团的取代都不 能改变聚合物的磁性特征．     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.