丙二酰二腙衍生的二氧化二钼(Ⅵ)配合物的合成、表征和晶体结构

本文报道了二氧杂钼(Ⅵ)配合物[MoO₂(H₂L)(H₂O)]的合成、表征和分子结构。该配合物是由马来酰二腙配体双(2-羟基-1-萘醛)丙二酰二腙(H₄L)与双(乙酰丙酮)二氧钼(Ⅵ)在甲醇中以1∶1的物质的量之比反应得到的。通过各种光谱(如IR、MS和NMR)对该配合物进行了表征。通过单晶X射线晶体学确定了配合物的结构。该配合物属于单斜晶系P2₁/c空间群。金属中心具有扭曲的八面体配位环境,与H₂L^2-的1个甲亚胺氮原子、2个末端氧基团、H₂L^2-的2个氧原子和配位水分子的1个氧原子相连。     

丙二酰二腙衍生的二氧化二钼(Ⅵ)配合物的合成、表征和晶体结构

本文报道了二氧杂钼(Ⅵ)配合物[MoO₂(H₂L)(H₂O)]的合成、表征和分子结构。该配合物是由马来酰二腙配体双(2-羟基-1-萘醛)丙二酰二腙(H₄L)与双(乙酰丙酮)二氧钼(Ⅵ)在甲醇中以1∶1的物质的量之比反应得到的。通过各种光谱(如IR、MS和NMR)对该配合物进行了表征。通过单晶X射线晶体学确定了配合物的结构。该配合物属于单斜晶系P2₁/c空间群。金属中心具有扭曲的八面体配位环境,与H₂L^2-的1个甲亚胺氮原子、2个末端氧基团、H₂L^2-的2个氧原子和配位水分子的1个氧原子相连。     

含硒杂环萘二酰亚胺衍生物的合成及其场效应性能研究

萘二酰亚胺(NDI)类化合物由于其较好的平面性和较强的接受电子能力,被广泛应用于有机场效应晶体管(OFETs)和有机太阳能电池中(OSCs)。然而,高迁移率的n型和双极性NDI类半导体材料较少。基于此,本文设计合成了核位硒杂环修饰的NDI衍生物,通过引入1,2-二硒苯和1,2-二硒萘基团,对其能级进行了有效的调控,获得了两个新型的窄带隙NDI衍生物。通过溶液旋涂法,制备了两种材料的底栅底接触场效应晶体管器件,二者在空气中都表现出n型半导体特性,退火温度为120℃时性能达到最优,分别为1×10~(-3)cm~2·V~(-1)·s~(-1)(4)和5×10~(-3)cm~2·V~(-1)·s~(-1)(5)。同时,通过原子力显微镜和X射线衍射对材料薄膜的退火过程进行了研究。     

p,p′-芳炔桥连的四联萘拓扑环芳分子的设计与合成

基于联萘衍生物手性构型高度稳定的特点, 以光学活性的(R)-2,2'-二乙炔基-1,1'-联萘为模板, 设计了3个有趣的拓扑环芳分子——含有4个手性联萘单元的(R,R,R,R)-2a～2c, 并探讨了它们的合成. 合成路线涉及三甲基硅(Me₃Si-)保护基的控制导入, 对位取代的芳基连接桥的链接, 保护基的脱去以及分子间偶合成环4个步骤. 用比旋光度([α]_D), MS, IR, UV-Vis, ¹H和¹³C NMR以及元素分析表征了这些化合物.     

吲哚方酸菁半导体在场效应晶体管中的应用

研究了2,3,3-三甲基-1-H-吲哚方酸菁的场效应性质, 通过X射线衍射证实了方酸菁分子内电荷分离结构以及分子间面面堆积模式, 并在Si/SiO₂基片上通过真空蒸镀和旋涂的方法制备了p型晶体管器件. 通过对器件性能与沟道形态的研究, 我们发现退火处理能促进方酸菁薄膜由无定形态向多晶态转变, 从而使薄膜晶体管的迁移率从10^-5 cm²?V^-1?s^-1量级提高到10^-3 cm²?V^-1?s^-1量级. 顶接触结构单晶器件获得了7.8×10^-2 cm²?V^-1?s^-1的迁移率. 未封装的方酸菁晶体管在大气中也表现出较好的稳定性.     

构建一维铜基配位聚合物作为锂离子电池正极材料

合成了一种新型的一维(1D)羰基配位聚合物[Cu (BGPD)(DMA)(H₂O)]·DMA (记为Cu-BD,H₂BGPD=N,N′-双(甘氨酰)均苯四甲酸二酰亚胺,DMA=二甲基乙酰胺),并考察了其用作锂离子电池正极材料的电化学性能。电化学测试结果表明,Cu-BD正极在50 mA·g^-1的电流密度下循环100圈后仍然保留50 mAh·g^-1的比容量,具有较好的循环稳定性。Cu-BD电极反应机理研究表明,BGPD^2-配体和Cu (Ⅱ)离子在充放电过程中都可能参与了电子转移过程。     

构建一维铜基配位聚合物作为锂离子电池正极材料

合成了一种新型的一维(1D)羰基配位聚合物[Cu(BGPD)(DMA)(H₂O)]·DMA(记为Cu-BD,H₂BGPD=N,N''-双(甘氨酰)均苯四甲酸二酰亚胺,DMA=二甲基乙酰胺),并考察了其用作锂离子电池正极材料的电化学性能。电化学测试结果表明,Cu-BD正极在50 mA·g^-1的电流密度下循环100圈后仍然保留50 mAh·g^-1的比容量,具有较好的循环稳定性。Cu-BD电极反应机理研究表明,BGPD配体和Cu(II)离子在充放电过程中都可能参与了电子转移过程。     

基于Cyclam衍生物的单核金属配合物的结构及核酸酶活性

以1,8-二甲基-1,4,8,11-四氮杂环十四烷为原料,以N,N'-二叔丁氧羰基-2-甲璜酰氧基-1,3-二氨基丙烷为烷基化试剂,合成了cyclam衍生物:1,8-二(N,N'-二叔丁氧羰基-1,3-二氨基异丙基)-4,11-二甲基-1,4,8,11-四氮杂环十四烷(L₁);及其对应的系列单核金属配合物,Zn(L₁)Cl₂ (1),Ni(L₁)Cl₂ (2)和Cu(L₁)Cl₂ (3);核磁结果表明,L₁为C2对称结构,且cyclam环上每一个亚甲基碳上的2个氢化学不等价;利用2D[¹H,¹⁵N]HSQC对比配体配位前后N-H化学位移的变化,确定配合物的结构是金属与配体cyclam环上的4个氮原子配位;利用变温核磁¹H NMR和¹³C NMR,结合2D[¹H,¹⁵N]HSQC核磁共振波谱表明,配合物1在溶液中主要以两种构型并存,并主要以trans-Ⅲ构型存在。此外,用凝胶电泳研究了配体与单核金属配合物对超螺旋pBR322质粒DNA切割活性;实验结果表明,配合物3在抗坏血酸存在的条件下具有核酸酶活性,而配体(L₁),配合物1和配合物2在实验条件下,无论是氧化切割还是水解切割都显阴性。     

多羟基甾醇25(R)-异螺甾环-5-烯-2β,3α,19-三醇的合成

以薯蓣皂素为原料, 经过磺酰酯化、N-溴代丁二酰亚胺(NBS)氧化加成、Pb(OAc)₄远程氧化关环、消去反应、间氯过氧苯甲酸(mCPBA)氧化、高氯酸开环及锌粉还原7步反应, 合成多羟基甾体25(R)-异螺甾环-5-烯-2β,3α,19-三醇. 并用IR, ¹H NMR, ¹³C NMR, MS及元素分析对各中间体及目标化合物进行了表征.     

不对称双二茂铁脲衍生物的合成、表征及电子传递性质

以二茂铁为原料,通过多步反应,首先合成了对称的桥联双二茂铁脲(5),再将其与胱胺反应,合成了一种新的不对称桥 联双二茂铁脲衍生物MeOOC-Fc-NH-CO-NH-Fc-CO-NH-(CH₂)₂-S-S-(CH₂)₂-NH₂ (7)(Fc：二茂铁)。对目标产物进行了红外、紫外、¹H NMR和MS表征;由于目标化合物7含有不对称的二茂铁脲这一特殊结构,采用循环伏安(CV)方法对化合物7的电子迁移特性进行了研究。结果表明2个二茂铁之间通过脲键传递电子,从而使2个二茂铁基团可以分别被氧化,它们的氧化电位差ΔE_o^?为181 mV,它们之间的稳定常数Kc为1 145。相对于对称的二茂铁脲(5)(ΔE_o^?=140 mV,K_c=207),这种不对称结构分子中2个二茂铁之间电子间的相互作用增强。     

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.