Self-assembly of metalloporphyrins: first TPP-bipy coordination polymer with CoII (TPP=meso-tetraphenylporphyrin and bipy=4,4´-bipyridine)

Póster presentado en: 11th International Symposium on Applied Bioinorganic Chemistry. 2-5 Diciembre 2011. Barcelona, España (ISABC 2011)

Fabrication of excitonic luminescent inorganic-organic hybrid nano- and microcrystals

Inorganic-organic (IO) hybrid nano- and microcrystals are fabricated by a low-cost, environmentally friendly and easily scaled-up route. Lead(II) iodide (PbI 2) nano/microcrystals are obtained by solvothermal techniques and subsequent IO hybrid (C 12H 25NH 3) 2PbI 4 crystals are produced by intercalation of the organic moiety. The hexagonally shaped crystals obtained range in size from 20 nm to ∼7 μm. Sequential stacking of inorganic/organic layers in these IO hybrid crystals results in strong room-temperature exciton photoluminescence, wherein the excitons are confined within the inorganic sheets. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

微/纳米结构氟化物溶剂热合成及其光学性质研究

本文主要利用Liquid-Solid-Solution（LSS）方法合成了一系列的碱土金属氟化物纳米粒子, 具有微米结构的Ba2ClF3体系以及复合金属氟化物NaMgF3纳米晶。利用X－射线衍射（XRD）、透射电镜（TEM）、扫描电镜（FE-SEM）、红外光谱（IR）等技术对合成材料的结构、形貌、组成等进行表征，采用紫外-可见吸收光谱、荧光光谱（PL）、荧光寿命等手段评价合成材料的光致发光性能；探讨了油酸作为表面活性剂在纳米晶形成过程中的作用，并阐述了纳米晶的生长过程及可能的生长机理。对氟化物的胶体溶液的发光性质作了研究，并提出了可能的发光机理。 采用LSS方法制备的一系列碱土金属氟化物（CaF2，SrF2，BaF2）纳米晶结晶完好，具有碱土金属氟化物体材料的立方相结构。制备所得的碱土金属氟化物纳米晶分别具有被截的八面体，立方体和立方片形貌，粒子尺寸较均匀，分布范围较窄。制备的纳米晶由于表面被油酸的长烷基链所包覆，可以溶于非极性溶剂如环己烷形成稳定透明的胶体溶液。三种纳米晶的环己烷胶体溶液在光致发光光谱中在400nm左右出现了一个较强的发射峰。这可能是由在纳米晶的形成过程中产生的缺陷和电子中心所造成的。 采用LSS方法在较低的温度下（160oC）成功地制备了一维Ba2ClF3六方微米棒。制备的Ba2ClF3微米晶结晶完好，具有其相应体材料的斜方六面体结构。由于斜方六面体相晶胞表现出六方相的特性，因此具有各向异性。在包覆剂油酸的作用下，生成一维的六方微米棒。制备的六方微米棒具有较好的分散性，光滑的棒表面以及清晰的棱。同时，油酸的加入，氢氧化钠量，反应物加入量以及反应时间均对形貌和尺寸有所影响。通过调节合成参数，我们成功了具有不同尺寸和长宽比的微米棒。 采用LSS方法制备了复合氟化物NaMgF3纳米晶。制备的NaMgF3纳米晶结晶完好，具有正交晶相的结构。粒子平均尺寸约为38.6 nm。所得的纳米晶可溶于环己烷溶剂形成稳定透明的胶体溶液，其胶体溶液在400 nm左右有一个强的发射峰。

Synthesis of Cu-In-S ternary nanocrystals with tunable structure and composition

Nearly monodisperse Cu-In-S ternary nanocrystals with tunable composition, crystalline structure, and size were synthesized by a hot-injection method using mixed generic precursors. Such ternary nanocrystals with zincblende and wurtzite structure were reported for the first time.

Synthesis and characterization of 1D Co/CoFe2O4 composites with tunable morphologies

1D Co/CoFe2O4 composites with tunable morphologies were fabricated by a facile solvothermal route in the presence of a surfactant poly(vinylpyrrolidone) (PVP); they may be very attractive for potential applications because of their outstanding soft magnetism.

A Unique Mn2Gd2 Tetranuclear Compound of p-tert-Butylthiacalix[4]arene

A calixarene complex with tetragonal (Mn2Gd2III)-Gd-II tetranuclear units was synthesized in solvothermal conditions, where the addition of a small amount of water was crucial for the formation of the target compound. In the structure, two tail-to-tail p-tert-butylthiacalixarenes are located in a C-shaped mode with a dihedral angle of 14.29 degrees but not in the conventional antiparallel arrangement and form a sandwich-like subunit with an in-between Mn2Gd2 unit. Both calixarenes assume similar cone shapes of C-2v symmetry but are pinched to different extents.

3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

Two Mn(2)(II)Ln(4)(III) (Ln = Gd, Eu) hexanuclear compounds of p-tert-butylsulfinylcalix[4]arene

Two 3d-4f heterometallic compounds of p-tert-butylsulfinylcalix[4] arene were synthesized by the solvothermal method and characterized by some hinged double-dumbbell-like subunits in which two perpendicular dumbbell entities were constructed by an in-between isosceles triangle Mn(II)Ln(2)(III), and two tail-to-tail calixarene molecules, and hinged by the lanthanide-sulfinyl group bonding. The magnetic properties of the title compounds were examined.

Self-Assembly from Two-Dimensional Layered Networks to Tetranuclear Structures: Syntheses, Structures, and Properties of Four Copper-Thiacalix[4]arene Compounds

Two new copper-thiacalix[4]arene compounds, [Cu-2(1)-Cl-2(H(4)TC4A)](CH3OH) (1) and [Cu(I)2Cl(2)(H(4)PTC4A)](CH3OH)(CHCl3)(0.5) (2) (where H(4)TC4A = p-tert-butylthiacalix[4]arene and H(4)PTC4A = p-phenylthiacalix[4]arene), were synthesized by the solvothermal method in the mixed CH3OH/CHCl3 (1: 1) solvent and reassembled in air at room temperature to two other structures, [(Cu4Cl3)-Cl-II(HCO2)(TC4A)(CH3-OH)(2)(H2O)](CHCl3)(CH3OH)(2.7) (3) and [(Cu4Cl4)-Cl-II(PTC4A)(CH3OH)(4)] (4), respectively. All these four compounds were characterized by TG analyses, FTIR spectroscopy, and singlecrystal X-ray diffraction analyses. Compounds 1 and 2 feature two-dimensional layered networks, while compounds 3 and 4 are assembled by some tetranuclear units.

Synthesis of Titania in Ethanol/Acetic Acid Mixture Solvents: Phase and Morphology Variations

The phase and morphology variations of titania prepared in ethanol/acetic acid mixture solvents have been systematically investigated. X-ray diffraction results and microscopy observations reveal that pure anatase aggregates consisted of small nanoparticles, pure rutile microspheres comprised of nanofibers, and their mixtures could be obtained by varying ratios of ethanol to acetic acid under solvothermal conditions. The contents of anatase and rutile in the mixed phases also vary with the ratios of ethanol to acetic acid. Field emission scanning electron microscopy and high resolution transmission electron microscopy results show that the two phases are separated from each other in final products and form aggregates with morphologies resembling to their pure phase products obtained under favorable conditions. The as-produced rutile nanofibers, either in pure phase or in mixed phases, tend to grow into hollow microspheres.

Synthesis and Characterization of One-Dimensional and Molecular M(tren)InAsS4 (M = Mn, Co, and Zn) Compounds with a Noncondensed AsS33- Unit

Four transition-metal-amine complexes incorporating indium thioarsenates with the general formula M(tren)InAsS4 (M=Mn, Co, and Zn) and a noncondensed AsS33- unit have been prepared and characterized. Single-crystal X-ray diffraction analyses show that compound 1 (M=Mn) crystallizes in the triclinic crystal system (space group: P (1) over bar) and consists of a one-dimensional (1D) inorganic (1)(infinity){[InAsS4](2-)} chain and [Mn(tren)](2+) groups bonded to the opposite sides of an eight-membered In2As2S4 ring along the backbone of the infinite inorganic chains. Compounds 2 (M=Mn), 3 (M=Zn), and 4 (M=Co) are isomorphous molecular compounds. They all crystallize in the monoclinic crystal system (space group: P2(1)/c). The Mn2+ cation of [Mn(tren)](2+) in 1 has a distorted octahedral environment, while the transition-metal cations of [M(tren)](2+) in the other three compounds locate in trigonal-bipyramidal environments.

Ordered magnetic core-manganese oxide shell nanostructures and their application in water treatment

In this paper, we have reported a facile method for the synthesis of ordered magnetic core-manganese oxide shell nanostructures. The process included two steps. First, manganese ferrite nanoparticles were obtained through a solvothermal method. Then, the manganese ferrite nanoparticles were mixed directly with KMnO4 solution without any additional modified procedures of the magnetic cores. It has been found that Mn element in the core can react with KMnO4 to form manganese oxide which acts as a seed for the in-situ growth of manganese oxide shells. This is significant for the controllable fabrication of symmetrical ordered manganese oxide shell structures. The shell thickness can be easily controlled through the reaction time. Transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction and energy-dispersive X-ray spectroscopy have been employed to characterize the products at different reaction time.