Synthesis and properties of conjugated hybrid tetrathiafulvalene dimers

The synthesis of new hybrid tetrathiafulvalene (TTF) dimers (11a-c) has been carried out by a Wittig-Horner reaction of the respective phosphonate esters (10a-c) with 2-(tetrathiafulvalenylvinyl)-9, 10-anthraquinone (9) prepared by olefination of formyltetrathiafulvalene (7) and the phosphonium salt of anthraquinone 8. Electrochemical studies show that the dimers 11a-c mainly retain the electrochemical properties of both TTF and the pi-extended TTF components, and most importantly, intramolecular electronic interactions between the two moieties are observed by cyclic voltammetry and Osteryoung square wave voltammetry. Semiempirical PM3 calculations reveal an almost planar geometry for the TTF and the benzene ring connected through the vinyl spacer. These compounds can form stable charge-transfer complexes with 2, 3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) showing a stoichiometry of 1:3 (D:A). Attempts to electrocrystallize the dimeric donors with different counteranions are discussed.     

Synthesis and properties of catechol-fused tetrathiafulvalene derivatives and their hydrogen-bonded conductive charge-transfer salts

Catechol-fused tetrathiafulvalene (TTF) derivatives have been designed and synthesized as a new type of π-electron donor molecules having two phenolic hydroxyl groups. Cyclic voltammetry measurements and quantum chemical calculations demonstrated the electronic effect of the direct fusion of the catechol unit to the TTF π-skeleton. In the charge-transfer (CT) salts with bromide or chloride anions, a one-dimensional hydrogen-bonded chain was formed by the intermolecular OH?X network between the catechol moieties and the halide anions. The slight dissimilarity of the hydrogen-bond distances for the two CT salts gave rise to the significant differences in their overall molecular arrangements and intermolecular interactions as well as the electrical resistivities.     

Design and synthesis of novel mesostructured metal-organic frameworks templated by cationic surfactants via cooperative self-organization

A novel design strategy to synthesize highly ordered hexagonally mesostructured metal-organic framework materials was successfully explored, which means the realization of directly cooperative self-assembly of metal ions, bridging ligands and surfactants in an aqueous system.     

Novel hybrid hetero-sandwich architectures via stoichiometric control of host-guest self-organization

Thiocyanate cadmium and methylviologen hybrid host-guest compounds give two novel multiple sandwich architectures with regular or irregular grids of the anionic layer in the structures as effected by the molar ratios of starting ingredients, and show evidence of charge-transfer to the organic dications.     

Development of electrospun metallic hybrid nanofibers via metallization

The metallized hybrid nanofiber webs were prepared by using a combined technology of electrostatic spinning and metallization. The electrospun polyurethane (PU) nanofibers were metallized with different thicknesses of copper layer via metal vapor deposition technique. The thickness of the copper layer, which ranges from 10 to 100 nm, was monitored and controlled. The resultant metallized hybrid nanofiber webs were characterized using field emission scanning electron microscopy (FE‐SEM), wide angle X‐ray diffraction (WAXD), and thermogravimetric analysis (TGA). FE‐SEM images demonstrated that the nanoscaled copper layers are well deposited on the surface of the PU nanofibers. TGA result indicated that the thermal stability of the metallized hybrid PU nanofibers was dramatically enhanced due to the barrier effects of thin metallic copper layer. WAXD data confirmed that the crystalline copper layers were well deposited onto the PU nanofibers. Moreover, the mechanical properties of the metallized hybrid PU nanofiber webs were increased with increase in the thickness of deposited copper layer. Unlike the organic PU nanofiber webs, it was observed that the metallized hybrid PU nanofiber webs showed higher conductive properties depending on the thickness of the deposited copper layer. Copyright © 2009 John Wiley & Sons, Ltd.     

Controllable growth of gold nanowires and nanoactuators via high-frequency AC electrodeposition

An electrochemical deposition method using high-frequency alternating current (AC) signal is reported here for the in situ synthesis and assembly of Au nanowires and nanoactuators on microelectrodes without using any masks or templates. High conductivity of 3.79 ± 0.14 × 10⁷ Ω^− 1 m^− 1 is achieved on the Au nanowires assembled between electrodes. Au nanoactuators with expansion ratio of more than 500% can be fabricated at higher frequency. The actuators can act as claws to grab SiO₂ nanoparticles in a water solution when driven by an alternating electric field. Disconnected nanowires and nanoparticles which self-aligned around the electrodes were also obtained at lower gold ion concentration, indicating a different current transfer mode in AC electrodeposition.     

Synthesis and dispersion of isolated high aspect ratio gold nanowires

We report the assembly properties of high density and high aspect ratio metal nanowire arrays (Au, Cu and Ag with diameters ranging from 40 to 250 nm) after release from the anodic alumina oxide (AAO) templates. Individual Ag and Cu nanowires were observed following release from the template, however, in the case of gold nanowires, the dispersion was dependent on size and aspect ratio. 40-100 nm gold wires aggregated to form bundles or disordered mats. We show that a simple cyanide-mediated release from the AAO template, results in isolated dispersion of wires even for the smallest wire diameters. Possible stabilising mechanisms for observed tendency of nanowires dispersion are discussed.     

Synthesis of flexible, ultrathin gold nanowires in organic media

Gold nanoparticles are very interesting because of their potential applications in microelectronics, optical devices, analytical detection schemes, and biomedicine. Though shape control has been achieved in several polar solvents, the capability to prepare organosols containing elongated gold nanoparticles has been very limited. In this work we report a novel, simplified method to produce long, thin gold nanowires in an organic solvent (oleylamine), which can be readily redispersed into nonpolar organic solvents. These wires have a characteristic flexible, hairy morphology arising from a small thickness (<2 nm) and an enormous length (up to several micrometers), with the possibility of adjusting the dimensions through modification of the growth conditions, in particular, the gold salt concentration. Despite their extreme aspect ratio, the wires are stable in solution for long periods of time but easily break when irradiated with high-energy electron beams during transmission electron microscopy.     

Synthesis of silver dendritic nanostructures protected by tetrathiafulvalene

Silver dendritic nanostructures protected by tetrathiafulvalene (TTF) were synthesized via reduction of silver ions with TTF in acetonitrile.     

Synthesis of self-standing Pd nanowires via galvanic displacement deposition

This work shows that it is possible to obtain self-standing Pd nanowires into anodic alumina membranes by a simple metal displacement deposition. By using a proper arrangement, specifically designed in order to optimize the process, polycrystalline Pd nanowires were deposited from a solution containing Pd(NH₃)₄(NO₃)₂ as precursor. Morphological analysis showed the formation of perfectly aligned nanowires with a uniform diameter throughout the entire length. This last parameter was controlled by both the deposition time and the ratio between the anodic area (active metal) and the cathodic area (pore bottom).     

Synthesis of ultrahigh-density ordered arrays of metallic nickel nanowires in mesoporous silica films

Two-dimensional (2D) mesoporous silica films were employed as a template to fabricate ultrahigh-density ordered arrays of metallic nickel nanowires via electroless deposition.     

A low-molecular-mass gelator with an electroactive tetrathiafulvalene group: tuning the gel formation by charge-transfer interaction and oxidation

A new low-molecular-mass gelator with one TTF and one urea group is described. It was found that the gel formation can be tuned by formation of CT complexes and oxidation.     

Synthesis and characterization of metallic copper nanoparticles via thermal decomposition

Copper oxalate was used as a precursor to prepare metallic copper nanoparticles by thermal decomposition. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and UV–Vis spectroscopy. XRD analysis revealed broad pattern for fcc crystal structure of copper metal. The particle size by use of Debye–Scherrer’s equation was calculated to be about 40 nm.     

Ultrathin gold nanowires can be obtained by reducing polymeric strands of oleylamine-AuCl complexes formed via aurophilic interaction

This Communication describes a facile route to the preparation of ultrathin gold nanowires using linear chains formed from [(oleylamine)AuCl] complex via aurophilic interaction. The linear chains, with AuI...AuI bonds as the backbone and surrounded by oleylamines, can group together to form bundles of polymeric strands. When the AuI was reduced to Au0 by reacting with Ag nanoparticles in hexane, the polymeric strands functioned as both the source of Au and the template to mediate the nucleation and growth of Au nanowires. Using this method, we were able to produce Au nanowires with an average diameter of approximately 1.8 nm and an aspect ratio of >1000 in high yields (approximately 70%).     

Synthesis of gold functionalized poly-bisvinylethyleneurea/silica hybrid materials

Novel gold/poly-(1,3-divinyl-imidazolid-2-one)/silica [poly-bisvinylethyleneurea (poly-BVU)/silica)] hybrid particles have been produced by adsorption and spontaneously occurring in situ reduction of Au(3+) cations on the surface of poly-BVU/silica hybrid particles. The successful functionalization of the poly-BVU/silica particles with gold nanoclusters has been evidenced by UV/vis and XPS spectroscopy as well as scanning electron microscopy. The size of the resulting gold clusters, estimated by means of the Mie-Drude theory on the full peak width at half-maximum of the surface plasmon UV/vis absorbance, correlates with the polymer content of the poly-BVU/silica hybrid particles used for the modification. Therefore, it is possible to control the size of the gold clusters simply by adjusting the monomer/silica ratio in the polymerization process, which corresponds with the polymer content of the hybrids.     

Growth of colloidal gold nanostars and nanowires induced by palladium doping

Gold-palladium nanocrystals with starlike shapes and high aspect ratio nanowires were grown in a surfactant solution. The incorporation of palladium into the growing gold nanostructures induced nanowire formation with high yield. Kinetic control of the metal deposition rate through tuning of the pH value to about 5 was crucial for the nanowire growth. The nanostructures were characterized by high-resolution electron microscopy and energy-dispersive X-ray spectroscopy. The Au-Pd nanowires were deposited on functionalized silicon wafers.     

Synthesis of nickel nanowires via electroless nanowire deposition on micropatterned substrates

Electroless nanowire deposition on micropatterned substrates (ENDOM) is a promising new technique by which to direct the synthesis and precise placement of metallic nanowires. ENDOM is generally applicable to the preparation of metallic, semiconducting, and even insulating nanowires on technologically relevant substrates, is inexpensive, and can achieve high growth rates. The deposited nanowires are ultralong (centimeters) and can be patterned in arbitrary shapes. We demonstrate ENDOM using the growth of nickel nanowires. By controlling the deposition time, the width of the nanowires can be varied from 200 to 1000 nm and the height can be varied from 7 to 20 nm.     

Synthesis and characterization of CePO_4 nanowires via microemulsion method at room temperature

Uniform CePO_4 nanowires with diameter of about 25 nm were synthesized by the water-in-oil microemulsion method at room temperature from cerous chloride,sodium orthophosphate,sodium chloride,cyclohexane,Triton X-100 and cetyltrimethyl ammonium bromide(CTAB).The crystal structure and morphology of the nanowires were characterized by XRD and TEM, respectively.The UV-vis absorption was detected by UV-vis spectrophotometer techniques.The results showed that as-prepared nanowires with the hexagonal phase have...