MCM-41-罗丹明B超分子功能材料的组装及其发光

随着化学及高新技术的发展,一门新兴的边缘学科超分子化学和器件正在引起理论和实验化学家的广泛重视.超分子化学可定义为由多个分子通过分子间非键合作用而形成的复杂但有组织的体系.     

Oxidation chemistry of poly(ethylene glycol)-supported carbonylruthenium(II) and dioxoruthenium(VI) meso-tetrakis(pentafluorophenyl)porphyrin

[Ru(II)(F(20)-tpp)(CO)] (1, F(20)-tpp=meso-tetrakis(pentafluorophenyl)porphyrinato dianion) was covalently attached to poly(ethylene glycol) (PEG) through the reaction of 1 with PEG and sodium hydride in DMF. The water-soluble PEG-supported ruthenium porphyrin (PEG-1) is an efficient catalyst for 2,6-Cl(2)pyNO oxidation and PhI==NTs aziridination/amidation of hydrocarbons, and intramolecular amidation of sulfamate esters with PhI(OAc)(2). Oxidation of PEG-1 by m-CPBA in CH(2)Cl(2), dioxane, or water afforded a water-soluble PEG-supported dioxoruthenium(VI) porphyrin (PEG-2), which could react with hydrocarbons to give oxidation products in up to 80 % yield. The behavior of the two PEG-supported ruthenium porphyrin complexes in water was probed by NMR spectroscopy and dynamic light-scattering measurements. PEG-2 is remarkably stable to water. The second-order rate constants (k(2)) for the oxidation of styrene and ethylbenzene by PEG-2 in dioxane-water increase with water content, and the k(2) values at a water content of 70 % or 80 % are up to 188 times that obtained in ClCH(2)CH(2)Cl.     

聚苯胺/介孔碳纳米线复合电极材料的制备和性能

以介孔碳纳米线为基体, 通过电化学方法制备了新型聚苯胺/介孔碳纳米线(PANI/MCFs)复合材料, 采用SEM和TEM等手段对样品的结构和形貌进行了表征. 结果表明, 聚苯胺均匀附在介孔碳纳米线表面, 并填充到纳米线介孔孔道中. 将复合材料组装成三电极体系超级电容器, 用循环伏安、 恒流充放电和交流阻抗等方法对材料的电化学性能进行了测试. 结果显示, 在1 mol/L H₂SO₄溶液中, 复合材料的比电容达到391 F/g, 其循环稳定性也得到显著提高.     

Supramolecular Self-Assembly of 1D and 3D Heterometallic Coordination Polymers with Triruthenium Building Blocks

Ru(3) (TSA)(6) (1; H(2) TSA=2-thiosalicylic acid), which bears six peripheral carboxylate groups and was isolated in the form [NEt(4) ](1.5) [Ru(3) (HTSA)(2) (TSA)(4) ](OAc)(0.5) ?3.5?H(2) O, serves as a building block for assembly of heterometallic coordination polymers. Treatment of 1 with [Fe(acac)(3) ] (acac=acetylacetonate) in EG/H(2) O (EG=ethylene glycol) afforded 1D Ru(3) -Fe coordination polymer 2 by means of the connection of the building block 1 through iron centers. Treatment of 1 with MnCl(2) in EG resulted in the formation of 1D Ru(3) -Mn(3) coordination polymer 3, which features self-assembled polynuclear linking units Mn(3) (OCH(2) CH(2) O)(3) , each of which contains a planar Mn(3) O(3) ring. By treating 1 with Gd(NO(3) )(3) and NaHCO(3) in EG, a 3D Ru(3) -Gd(6) coordination polymer 4 was obtained; this 3D coordination polymer features unprecedented Gd(6) (μ(3) -CO(3) )(4) units. The magnetic properties of 1-4, along with DFT calculations on the electronic structure of 1, are also described.     

以含铬类水滑石型层状化合物为模板制备硫化物半导体纳米晶

采用类水滑石型混合金属氢氧化物(CdCr-LDH和ZnCdCr-LDH)为前驱体, 通过气-固反应方法, 制备了根植于层状氢氧化物层板中的硫化镉纳米晶和硫化镉/硫化锌复合纳米晶, 通过改变前驱体(CdCr-LDH)中镉和铬的摩尔比可以调控硫化镉纳米晶的粒径.     

Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins

Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3) mol(-1) s(-1). An X-ray structure determination of complex 4 reveals an O- rather than N-coordination of the aziridine axial ligand. The fact that the N-tosylaziridine in 4 does not adopt an N-coordination mode disfavors a concerted pathway in the aziridination by a tosylimido ruthenium porphyrin active species.     

铁（Ⅱ）卟啉二胺配合物的合成和表征

已报道合成的二价铁叶琳配合物主要集中在毗陡、咪唑、NO等配体上．有机胺虽然是配位化学中一类极为经典的配体，但合成金属叶琳胺类配合物的报道却为数甚少，据我们所知，仅限于Ru[1]、Rh[3]、Os[3]等配合物．迄今还未见合成铁（Ⅱ）卟啉胺类的报道．本文通过引入强氧化...     

Tunable Surface Electric Field of Electrocatalysts via Constructing Schottky Heterojunctions for Selective Conversion of Trash Ions to Treasures

Surface electric field of catalyst is widely recognized as one of the key points to boost catalytic activity. However, there is still a lack of convenient ways to tune the surface electric field to selectively boost the catalytic conversions of different types of reactants in specific catalytic reactions. Here, we introduce a conceptually new method to tune the surface electric field of electrode materials by adjusting the number and density of heterojunctions inside. Both theoretical and experimental results prove that the well-designed surface electric field of an electrocatalyst plays a key role in facilitating pre-adsorption and/or activation of reactants for selective conversion of trash ions to useful products in hydrogen and oxygen evolution reactions as well as NO_x⁻ reduction reactions.     

Synthesis of amphiphilic superparamagnetic ferrite/block copolymer hollow submicrospheres

Self-assembly can be a powerful, but simple, synthetic method for the fabrication and surface modification of nanometer- to micrometer-sized hollow spheres. Here we report a facile route for preparation of submicrometer ferrite hollow spheres which are amphiphilic and superparamagnetic. This unique approach involves the formation of ferrite nanocrystals and the simultaneous self-assembly of nanocrystals and block copolymer PEO-PPO-PEO into hollow spheres. Furthermore, this approach is general for the preparation of a series of ferrite hollow spheres, including Fe3O4, Co1-xFe2+xO4, and Mn1-xFe2+xO4. Unlike conventional hollow spheres, which are either hydrophobic or hydrophilic, the products we obtained exhibit excellent dispersibility in both polar and nonpolar solvents.     

Reactivity of dioxoosmium(VI) porphyrins toward arylhydrazine. Isolation of hydrazidoosmium and amidoosmium porphyrins

Reactions of dioxoosmium(VI) porphyrins [Os(VI)(Por)O(2)] with excess 1,1-diphenylhydrazine in tetrahydrofuran at ca. 55 degrees C for 15 min afforded bis(hydrazido(1-))osmium(IV) porphyrins [Os(IV)(Por)(NHNPh(2))(2)] (1a, Por = TPP (meso-tetraphenylporphyrinato dianion); 1b, Por = TTP (meso-tetrakis(p-tolyl)porphyrinato dianion)), hydroxo(amido)osmium(IV) porphyrins [Os(IV)(Por)(NPh(2))(OH)] (2a, Por = TPP; 2b, Por = TTP), and bis(hydrazido(2-))osmium(VI) porphyrin [Os(VI)(Por)(NNPh(2))(2)] (3c, Por = TMP (meso-tetramesitylporphyrinato dianion)). The same reaction under harsher conditions (in refluxing tetrahydrofuran for ca. 1 h) gave a nitridoosmium(VI) porphyrin, [Os(VI)(Por)(N)(OH)] (4b, Por = TTP). Oxidation of 1a,b with bromine in dichloromethane afforded bis(hydrazido(2-)) complexes [Os(VI)(TPP)(NNPh(2))(2)] (3a) and [Os(VI)(TTP)(NNPh(2))(2)] (3b), respectively. All the new osmium porphyrins were identified by (1)H NMR, IR, and UV-vis spectroscopy and mass spectrometry; the structure of 2b was determined by X-ray crystallography (Os-NPh(2) = 1.944(6) A, Os-OH = 1.952(5) A).