苯甲酰水杨酸铽与PVK混合体系的发光特性

合成了一类以苯甲酰水杨酸（benzoyl salicylic acid,BSA)为第一配体，邻菲罗啉（1,10-phenanthroline,Phen)为第二配体的稀土铽配合物，将导电高分子材料PVK引入到配合物中，制成了结构为ITO／PVK：Tb(BSA)3phen/PBD/Alq/LiF/Al电致发光器件，并对该配合物的吸收特性及电致发光和光致发光性能进行了研究，实验数据表明在PVK与Tb(BSA)3phen之间存在着Forster能量传递，该配合物具有很好的光致发光和电致发光性能。本文同时比较了几种不同PVK掺杂浓度对于器件性能的影响。     

一类新型稀土配合物的合成与发光特性研究

合成了一类新型稀土配合物Eu(asprin)3phen和Tb(asprin)3phen,并将其掺杂到导电聚合物PVK中,制成结构了为ITO／PVK：RE配合物／LiF/Al的电致发光器件。很明显,在相同掺杂比例下,前者的电致发光中PVK发射所占比例较大,而后者的电致发光中PVK的发射几乎全部被覆盖掉了,进一步研究发现它们的光致发光中也有同样现象存在,这表明具有同等配体的此类铕、铽配合物的特性存在很大差别,并对这一差别作了初步讨论。     

共掺杂稀土配合物Tb0.5Eu0.5(asprin)3phen电致发光的研究

合成了共掺杂稀土配合物Tb0.5Eu0.5(asprin)3phen，将其掺杂到导电聚合物PVK中，制成结构为ITO／PVK：RE配合物／PBD／Al的电致发光器件，与PVK：Eu(asprin)3phen体系为发光层的相同结构的器件相比，我们发现铽离子的引入能猝灭PVK的发光，增强铕的发光，而Tb3 本身的发光很弱，几乎看不到，说明Pb3 在其中起到能量的中间传递作用，促进了PVK到Eu^3 的能量传递，本文就器件的发光特性及掺杂体系的能量传递进行了初步讨论。     

铽配合物TbY(o-MBA)6(phen)2与PVK掺杂体系的发光性质研究

合成了一种新型的稀土铽配合物材料TbY(o-MBA)6(phen)2,把它作为发光材料应用于有机电致发光中.把铽配合物掺杂在导电聚合物PVK中采用旋涂法制得发光层,并利用AlQ作为电子传输层制作了多种结构的电致发光器件 器件A,ITO/PVK∶TbY (o-MBA)6(phen)2/LiF/Al;器件B,ITO/PVK∶TbY (o-MBA)6(phen)2/AlQ/LiF/Al;器件C,ITO/PVK∶TbY (o-MBA)6(phen)2/BCP/AlQ/LiF/Al.对器件A和B得到了纯正的、明亮的Tb3+离子的绿光发射,4个特征峰分别对应着能级5D4到7Fj(j=6,5,4,3)的跃迁,而PVK的发光完全被抑制.研究了掺杂体系的光致发光性能和电致发光性能,认为在光致发光中,铽的发光主要来源于PVK到稀土配合物的Frster能量传递.而在电致发光中,铽的发光主要来源于稀土配合物直接捕获载流子形成激子复合发光.并通过优化选择得到了发光性能较好的器件B,其最大亮度在14 V时达到213 cd·m-2.     

一种新型共掺杂稀土配合物Gd0.5Eu0.5(TTA)3Dipy的电致发光特性

制备了一类以α-噻吩甲酰基三氟丙酮(TTA)为第一配体、2,2′-联吡啶(Dipy)为第二配体的共掺杂铕钆配合物Gd0.5Eu0.5(TTA)3Dipy。用其作为发光层材料制作了电致发光器件:ITO/PVK:Gd0.5Eu0.5(TTA)3Dipy/PBD/Al。讨论并证明了Gd3 与Eu3 之间存在F rster能量传递。研究了铕钆配合物与PVK共掺杂体系的激发光谱和光致发光谱,发现两者之间存在着能量转移,说明Gd3 的加入抑制了PVK自身的本征发光,促进了PVK到Eu3 的能量传递,得到了单色性很好的红光。     

稀土配合物Tb(p-MBA)3phen的有机电致发光

合成了一种新型的稀土铽配合物材料Tb(p-MBA)3phen,把它作为发光材料应用于有机电致发光中.把铽配合物掺杂在导电聚合物PVK中采用旋涂法制得发光层,并利用AlQ作为电子传输层制作了单层、双层有机电致发光器件:器件1(ITO/PVK):Tb(p-MBA)3phen/Al;器件2(ITO/PVK):Tb(p-MBA)3phen/AlQ/LiF/Al,得到了纯正的、明亮的Tb3 离子的绿光发射,4个特征峰分别对应着能级5D4到7Fj(j=6,5,4,3)的跃迁,而PVK的发光完全被抑制.研究了两种器件的电致发光性能,并通过选择AlQ的厚度得到了发光性能较好的器件,其最大亮度在20 V时达到152 cd·m-2.     

PVK掺杂稀土铕配合物的电致发光中的能量传递过程

将Michler‘s Ketone(MK)作为协同配体与一种β－双酮类稀土配合物Eu(fod)3的氯仿溶液混合，两者有效配合生成一种新的稀土配合物Eu(fod)3MK，它的吸收谱中有一Michler‘s Ketone和Eu(fod)3都不具有的新的吸收峰，吸收边在450nm附近。这一新的吸收峰与PVK的发射谱有很好的重叠，从而使能量可以有效地通过Forster能量转移方式由PVK传递给稀土配合物。将这种新的稀土配合物掺杂到导电聚合物PVK中，并以它们为发光层制成电致发光器件。结果表明：加入协同配体后的光致发光和电致发光中，PVK的发射均被有效抑制。这说明MK贩加入大大提高了由聚合的基质向稀土配合物进行能量传递的效率。     

铕镧共掺稀土配合物Eu0.5La0.5(TTA)3phen与PVK共混体系发光特性的研究

合成了一种新型的稀土铕配合物Eu0.5La0.5(TTA)3phen,把它作为发光材料应用于有机电致发光中.把铕配合物与高分子导电聚合物共混制得混合溶液,然后用旋涂的方法制得了发光层.实验中制备了单层、双层器件,讨论了器件的优化条件,并用能级图探讨了Eu0.5La0.5(TTA)3phen与PVK共混体系光致、电致发光的能量传递机制.优化后的双层器件,开启电压为6.5 V,在电压12.5 V,电流密度为68.48 mA*cm-2时器件达到最大亮度238.4 cd·m-2,发光效率0.35 cd·A-1.     

钐、铕-2,4-二氯苯氧乙酸的二元、三元配合物的合成及荧光性能

以2,4-二氯苯氧乙酸为第一配体、1,10-菲罗啉为第二配体,合成了钐、铕的二元、三元配合物。通过元素分析、EDTA络合滴定及热重分析,确定了配合物的通式为RE(DCP)3.H2O,RE(DCP)3phen(RE=Sm,Eu;DCP=2,4-二氯苯氧乙酸根;phen=邻菲罗啉);测定了配合物红外光谱、紫外光谱、荧光光谱;研究了配合物的热稳定性。结果表明,三元配合物较二元配合物稳定;Eu(DCP)3.H2O和Eu(DCP)3phen具有荧光性能。     

铽配合物Tb(o-BBA)3(phen)有机电致发光研究

合成了一种新的稀土配合物邻苯甲酰苯甲酸-1，10-菲罗啉-铽（Tb（o-DDA）3（phen））并用于有机电致发光。研究了Tb（o-DDA）3（phen）与PVK混合薄膜的光敛发光特性，找出了PVK：Tb的最佳比例为3：1。制备了结构为ITO／PVK：Tb／Al的单层电致发光器件，得到了铽离子的特征光谱，其电流-电压特性（I-V）在一定电压范围内符合空间电荷限制电流机制。研究结果表明稀土铽配合物Tb（o-BBA）3（phert）掺杂PVK体系的光致发光是源于PVK到Tb配合物的能量传递及稀土Tb配合物的直接激发两种作用机制，而电致发光以载流子俘获为主。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

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.