稀土配合物分子组装及其性质研究

分子组装技术是一种在分子水平上进行的有序薄膜组装技术,包括Langmuir-Blodgett(LB)膜技术及自组装技术.该论文中,对稀土配合物及稀土杂多化合物的分子组装进行了系统的研究,取得了一些令人感兴趣的研究结果:合成了Na<,9>EuW<,10>O<,36>,Na<,9>DyW<,10>O<,36>,Na<,9>SmW<,10>O<,36>,K<,13>Eu(SiW<,11>O<,39>)<,2>,K<,13>Eu(GeW<,11>O<,39>)<,2>,K<,15>Eu(BW<,11>O<,39>)<,2>等稀土多金属氧酸盐,用LB膜技术将其组装入双十八烷基二甲基溴化铵(DODA)和十八胺(ODA)分子中,得到稀土杂多化合物LB膜.以稀土离子为亚相,制备了邻十六酰基苯甲酸-稀土(铽和铕)和对十六烷氧基苯甲酸铽LB膜.以1,2-二羟基苯-3,5-二磺酸铽(Tiron-Tb)为亚相,制备了DODA/Tiron-TbLB膜.以3-氨丙基三乙氧基硅烷为前驱体,制备了Na<,9>EuW<,10>O<,36>,Na<,9>DyW<,10>O<,36>的自组装膜.荧光光谱研究表明,在自组装膜中配体能将能量有效地传递给稀土离子.

Fabrication of fibril like aggregates by self-assembly of block copolymer mixtures via interpolymer hydrogen bonding

This paper describes the formation of fibril like aggregates from the self-assembly of block copolymer mixture (polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) and polystyrene-b-poly(acrylic acid) (PS-b-PAA)) via interpolymer hydrogen bonding in nonselective solvent. The hydrogen bonding between P4VP and PAA in chloroform leads to the formation of complex. When all the pyridine units in P4VP were all hydrogen bonded to acrylic acid in PAA, the formed complex is insoluble, resulting in the formation of spherical micellar aggregates and nanorods.

Assembly of 12-tungstosilicic acid and 4-aminobenzo-15-crown-5 ether based on the electrostatic attraction through bridging of oxonium ions on different substrates

Based on the electrostatic attraction Keggin-type polyoxometalate H4SiW12O40 (SiW12) and small molecule 4-aminobenzo-15-crown-5 ether (4-AB15C5) were alternately deposited on poly (allylamine hydrochloride) (PAH)-derived indium tin oxide (ITO) substrate through a layer-by-layer (LBL) self-assembly, forming a supramolecular multilayer film (film-A). SiW12 was also deposited on a glassy carbon electrode (GCE) derived by 4-AB15C5 via covalent bonding in 0.1 M NaCl aqueous solution and formed a composite monolayer film (film-B). UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy measurements demonstrated that the interactions between SiW12 and 4-AB15C5 in both two film electrodes were the same and caused by the bridging action of oxonium ions. But, the nanostructure in the two film electrodes was different. 4-AB15C5 in film-A was oriented horizontally to ITO substrate, however, that in film-B was oriented vertically to GCE. Namely film-A corresponded to a layer structure, and film-B corresponded to an intercalation structure.

Assembly of one-dimensional organic luminescent nanowires based on quinacridone derivatives

The quinacridone derivatives N,N'-dialkyl-1,3,8,10-tetramethylquinacridone (CnTMQA, n = 6, 10, 14) were used as building blocks to assemble luminescent nano- and microscale wires. It was demonstrated that CnTMQA with different lengths of alkyl chains display obviously different wire formation properties. C10TMQA and C14TMQA showed a stronger tendency to form 1-D nano- and microstructures compared with C6TMQA. The C10TMQA molecules could be employed to fabricate the wires with different diameters, which exhibited a size-dependent luminescence property. The emission spectrum of the C10TMQA wires with diameters of 200-500 nm shows a broad emission band at 560 nm and a shoulder at around 535 nm, while the emission spectrum of the C10TMQA wires with diameters of 2-3 mu m reveals a narrower emission band at 563 nm. For the CnTMQA-based samples with different morphologies, the emission property change tendency agrees with that of the powder X-ray diffraction patterns of these samples.

电荷转移配合物薄膜制备方法和结构表征的研究进展

回顾了与Langmuir-Blodgett(LB)技术有关的电荷转移配合物薄膜的各类制备方法、结构表征结果,并比较了制备方法对薄膜结构的影响.例如,将LB膜C18H37TCNQ(电子受体)插入到电子给体3,3',5,5'-tetramethylbenzidine(四甲基联苯胺,TMB)的石油醚溶液中进行掺杂,制备了TMB·C18H37TCNQ电荷转移配合物薄膜.在这种薄膜中,给体和受体以面对面的方式堆积,两者的环平面与基片平面接近垂直.而采用硬脂酸和C18H37TCNQ的混合LB膜通过类似的掺杂路线制备的TMB·C18H37TCNQ薄膜的结构发生了一些变化,例如其长的烃链C18H37更加垂直于基片平面.通过比较以前的各种实验结果可以得出以下结论:电荷转移配合物的结构可以通过制备方法得到控制.

Luminescent sol-gel thin films based on europium-substituted heteropolytungstates

Polyester thin films containing europium-substituted heteropolytungstate were obtained on quartz plate by the sol-gel method. The films exhibited the characteristic emission bands of the europium ion. The red to orange intensity ratio (R:O) of Eu3+ in the films increased as compared to the corresponding heteropolytungstate solids. The fluorescence lifetime of europium is shorter in the thin film than in the heteropolytungstate solid. The results indicated that the formation of europium-substituted heteropolytungstate/polyester thin film has great effect on the luminescence of europium- substituted heteropolytungstate.

Self-assembled monolayer growth of octanol on mica: Atomic force microscopy and Fourier-transform infrared spectroscopy studies

The growth kinetics of self-assembled monolayers formed by exposing freshly cleaved mica to octanol solution has been studied by atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). AFM images of samples immersed in octanol for varying exposure times showed that before forming a complete monolayer the octanol molecules aggregated in the form of small islands on the mica surface. With the proceeding of immersion, these islands gradually grew and merged into larger patches. Finally, a close-packed film with uniform appearance and few defects was formed. The thickness of the final film showed 0.8 nm in height, which corresponded to the 40degrees tilt molecular conformation of the octanol monolayer. The growth mechanisms consisted of nucleation, growth, and coalescence of the submonolayer films. The growth process was also confirmed by FTIR. And the surface coverage of the submonolayer islands estimated from AFM images and FTIR spectra as a function of immersion time was quite consistent.

Selective penetration of liquid-phase organic probe molecules into SAM of 2-mercapto-3-n-octylthiophene

An inherently disorganized self-assembled monolayer (SAM) of 2-mercapto-3-n-octylthiophene (MOT) has been formed on a gold bead electrode from its dilute ethanolic solution. The disorganization of the monolayer is attributed to the loose packing of the aliphatic chains of the MOT adsorbates, which results from a large difference in dimension/or cross-sectional area between the head (thiophene thiolate) and the tail (alkane chain) groups. Electrochemical measurements including ac impedance spectroscopy and metal underpotential deposition have shown that the monolayer is almost pinhole free. However, the MOT SAM can be penetrated by an organic probe molecule with affinity for the alkane chain part of the monolayer. Some typical probe molecules with different size and hydrophilicity have been employed to assess the permselectivity of the monolayer. Measurement results demonstrate that the ability of the employed probe molecules to penetrate into the monoalyer is mainly dominated by their hydrophilicity/or hydrophobicity. The results presented here suggest the potential application of MOT monoalyer to effectively modify the electrode surface for several research areas such as electrochemical sensors, electrocatalysis, electroanalysis, and supported hybrid bilayer membranes.

Synthesis, characterization and fabrication on a glassy carbon electrode of a tetra-iron substituted sandwich-type pentadecatungstodiarsenate heteropolyanion

A novel sandwich-type compound, Na-12[Fe-4(H2O)(2)(As2W15O56)2].41H(2)O, has been synthesized. The compound was well-characterized by means of IR, UV-vis, W-183 NMR and elemental analyses. The compound crystallizes in the triclinic, P (1) over bar symmetry group. The structure of the compound is similar to that of Na-16[M-4(H2O)(2)(As2W15O56)(2)].nH(2)O (M = Cu, Zn, Co, Ni, Mn, Cd), and consists of an oxo-aqua tetranuclear iron core, [(Fe4O14)-O-III(H2O)(2)], sandwiched by two trivacant alpha-Wells-Dawson structural moieties, alpha-[As2W15O56]. Redoxelectrochemistry of the compound has been studied in buffer solutions at pH = 4.7 using polarography and cyclic voltammetry ( CV). The compound exhibited four one-electron couples associated with the Fe(III) center followed by three four-electron redox processes attributed to the tungsten-oxo framework. The compound-containing monolayer and multilayer films have been fabricated on a 4-aminobenzoic acid modified glassy carbon electrode surface by alternating deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/-). CV, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and atomic force microscopy (AFM) have been used to characterize the multilayer films.

Multifunctional organic-inorganic multilayer films of tris(2,2 '-bipyridine)ruthenium and decatungstate

A new multifunctional multilayer films consisting of tris(2,2'-bipyridyl)ruthenium(II) (Rubpy) and sodium decatungstate (W-10) have been prepared by the layer-by-layer (LbL) self-assembly method on ITO substrate. X-ray photoelectron spectra (XPS) confirmed the existence of W10 and Rubpy. Cyclic voltammetry (CV) and UV-Vis spectroscopy demonstrated the uniform assembly of (W-10/Rubpy) multilayer films. The multilayer films possess electrocatalytic activities on the reduction of iodate and oxidation of oxalate. Moreover, the films exhibited electrochemiluminescence (ECL) with tripropylamine (abbreviated as TPA) as the coreactant and the ECL response was proportional to the number of (W-10/Rubpy) layers. These characteristics of the multilayer films might find potential applications in the field of sensors and materials fields.

Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Molecular construction of oriented crystalline NaMnF3 and KMnF3 with perovskite structures at room temperature

In this work. we report the fabrication of high-quality (101)-oriented orthorhombic NaMnF3 and (100)-oriented cubic KMnF3 perovskites via an organic monolayer template at room temperature. The controlled crystallization under the organic monolayer template is explained in terms of the electrostatic interactions and beneficial lattice matching between the organic template and the ions undergoing nucleation. The present study is of great importance in the preparation of oriented perovskite materials as well as in the understanding of the mechanism for organic-template-directed crystallization.

LB films of 2-n-heptadecanoylbenzoic-rare earth and their luminescence properties

Several ultrathin luminescent Langmuir-Blodgett (LB) films have been prepared by using the subphase containing the rare earth ions (Eu3+, Tb3-). The effect of the rare earth ions on the monolayer of 2-n-heptadecanoylbenzoic acid (HBA) was investigated. IR and UV spectra showed the rare earth ions were bound to the carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction. UV absorbance intensity increases linearly with the number of LB films layers, which indicate that the LB films are homogeneously deposited. The LB films can give off strong fluorescence. and the signal can be detected from a single layer. The characteristic luminescence behaviors of LB films have been discussed compared with those of the complexes.

Luminescence properties of LB films based on heteropolytungstate of rare earth

In this work, the LB films based on heteropolytungstate of Dy and Sm have been prepared. The X-ray diffraction shows the LB films have a highly ordered lamella structure. The luminescence characteristics of the LB films were studied. The charge transfer bands of LB films are in higher energies than those of the corresponding solids. It is noticed that the yellow to blue intensity ratio (Y:B) of Dy3+ in the LB films is different from that of the solid. The differences in the spectra show that the Dy3+ site symmetry in LB film was changed due to the interaction between the surfactant and the polyanions. The differences could also be found in the luminescence spectra of the LB films of Sm complex.

Preparation and luminescence properties of LB films based on 4-hexadecyloxybenzoic terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb3+ were prepared. The monolayer behavior of 4-hexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.