Photochromic inorganic-organic multilayer films based on polyoxometalates and poly(ethylenimine)

Novel photochromic inorganic-organic multilayers composed of polyoxometalates and poly(ethylenimine) have been prepared by the layer-by-layer (LbL) self-assembly method. The growth process, composition, surface topography, and photochromic properties of the multilayer films were investigated by UV-visible and Fourier transform infrared spectroscopy, atomic force microscopy, electrospin resonance (ESR), and X-ray photoelectron spectroscopy (XPS). Irradiated with ultraviolet light, the transparent films changed from colorless to blue. Moreover, the blue films showed good reversibility of photochromism, and could recover the colorless state gradually in air, where oxygen plays an important role in the bleaching process. On account of the ESR and XPS results, parts of W6+ in multilayers were reduced to W5+, which exhibited a characteristic blue; a possible photochromic mechanism can be speculated. This work provides basic guideline for the assembly of multilayers with photochromic properties.

Synthesis, crystal structure, and magnetic properties of {[Cu(oxbe)]Mn(H2O)[Cu(oxbe)(DMF)]}(n)center dot nDMF center dot nH(2)O: From dissymmetrical mononuclear entities to a 3D heterometallic supramolecular coordination polymer

Self-assembly of the building block [Cu(oxbe)](-) with Mn(II) led to a novel coordination polymer {[Cu(oxbe)]Mn(H2O)(Cu(oxbe)(DMF)]}(n).nDMF.nH(2)O, where H(3)oxbe is a new dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)-oxamido and DMF = dimethylformamide. The crystal forms in the triclinic system, space group P(1)over-bar, with a = 9.260(4) angstorm, b = 12.833(5) angstrom, c = 15.274(6) angstrom , alpha = 76.18(3)degrees, beta = 82.7(3)degrees, gamma = 82.31(3)degrees, and Z = 2. The crystal structure of the title complex reveals that the two-dimensional bimetallic layers are constructed of (CuMnII)-Mn-II-Cu-II chains linked together by carboxylate bridge and hydrogen bonds help to produce a novel three-dimensional channel-like structure. The magnetic susceptibility measurements (5-300 K) were analyzed by means of the Hamiltonian (H)over-cap = -2J(S)over-cap (Mn)((S)over-cap(Cu1) + (S)over-cap(Cu2)), leading to J = -17.4 cm(-1).

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.

How to form regular polymer microstructures by surface-pattern-directed dewetting

The substrates with regular patterns of self-assembly monolayers (SAMs) produced by microcontact printing with octadecyltrichlorosilane (OTS) was employed to direct thin polystyrene dewetting to fabricate ordered micrometer scale pattern. The pattern sizes and pattern fashion can be manipulated by controlling the experimental parameters. The pattern formation mechanisms have been discussed. The dewetting pattern can be transferred to form PDMS stamp for future microfabrication process.

Patterning thin polymer films by surface-directed dewetting and pattern transfer

The pattern evolution processes of thin polystyrene (PS) film on chemically patterned substrates during dewetting have been investigated experimentally. The substrates have patterns of self-assembly monolayers produced by microcontact printing with octadecyltrichlorosilane. Optical microscopy and atomic force microscopy images reveal that ordered micrometer scale pattern can be created by surface direct dewetting. Various pattern sizes and pattern complexities can be achieved by controlling the experimental parameters. The dewetting pattern has been transferred to form PDMS stamp for soft lithography.

Pattern formation in polymer films under the mask

This paper presents a straightforward method for patterning thin films of polymers, i.e. a prepatterned mask is used to induce self-assembly of polymers and the resulting pattern is the same as the lateral structures in the mask on a submicrometre length scale, The patterns can be formed at above T-g + 30 degreesC in a short time and the external electric field is not crucial. Electrostatic force is assumed to be the driving force for the pattern transfer. Viscous fingering and novel stress-relief lateral morphology induced under the featureless mask are also observed and the formation mechanisms are discussed.

From dissymmetrical mononuclear entities to centrosymmetrical heterotrinuclear complex with 2D supramolecular structure: synthesis, characterization, crystal structure, and magnetic properties

A new centrosymmetrical heterotrinuclear complex, {[Cu(oxbe)](2)Co(H2O)(2)}.2DMF.DMA with 2D supramolecular structure, has been obtained by the self-assembly of a dissymmetrical building block [Cu(oxbe)](-) with bivalent metal ion Co2+, where H(3)oxbe is dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)oxamido, DMF = dimethylformamide, DMA = dimethylamine. Its structure was determined by single crystal X-ray analysis. The molecular structure is centrosymmetrical with the cobalt atom lying on an inversion center. Through the hydrogen bonds and d-pi stacking interactions, a 2D supramolecular structure is formed. This study exemplifies a new method for the assembly of supramolecular structure using a dissymmetrical brick. Magnetic susceptibility measurements (5-300 K) indicate that the central cobalt and terminal copper metal ions are antiferromagnetically coupled with J = -23.1 cm(-1).

Metal-containing molecular wires and their electron transportation properties

Metal-containing conjugated bisthioester 1 was synthesized. It was fabricated into "gold electrode - molecular wires monolayers - gold nanoparticles" junction using self-assembly and nanoparticles deposition techniques. The junction is suitable for investigating the electron transportation property of molecular wires.

Amplified DNA detection sensitivity using streptavidin-biotinylated protein complex: Characterization by electrochemical impedance spectroscopy

Thiol-terminated oligonucleotide was immobilized to gold surface by self-assembly method. A novel amplification strategy was introduced for improving the sensitivity of DNA. hybridization using biotin labeled protein-streptavidin network complex. This complex can be formed in a cross-linking network of molecules so that the amplification of the response signal will be realized due to the big molecular size of the complex. It could be proved from the impedance technique that this amplification strategy caused dramatic improvement of the detection sensitivity. These results give significant advances in the generality and sensitivity as it is applied to biosensing.

Synthesis and characterization of ferrocene-terminated ruthenium phenylacetylide complexes with alligator clips

Ferrocene-terminated trans/Ru(dppm)(2) (dppm=Ph2PCH2PPh2)-contained molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.

A cunning strategy in design of polymeric nanomaterials with novel microstructures

A relative approach, based on the dynamic density functional theory, for simulating the solvent evaporation rate dependence of self-assembly process of block copolymers in solution is proposed. The di- and triblock copolymers are first chosen as the candidates for exploration of novel microstructures. The results reveal that asymmetrical block copolymers with unequal block length, which generally exhibit disordered microdomain patterns in melts, have the ability to assemble into periodic ordered microdomain patterns by properly controlling solvent evaporation rate, e.g., diblock copolymers may assemble into lamellar microstructures with lamellar thickness proportional to individual block length. This simulation suggests a strategy of design and manufacture of polymeric nanomaterials with novel microstructures.

In situ controllable synthesis of polyoxometalate nanoparticles in polyelectrolyte multilayers

Size-controlled Ag3PW12O40 nanoparticles have been synthesized in situ in polyelectrolyte multilayer thin films via layer-by-layer self-assembly.

A novel photochromic multilayer based on preyssler's cluster

A novel photochromic multilayer film containing polyoxometalates has been fabricated using layer-by-layer self-assembly.

Investigation of electrochemical charging behaviors of "naked" gold nanoparticles ensembles in aqueous media

Gold nanopartides were Immobilized onto the electrode surface by simple self-assembly technique. Interestingly, the ensembles of these nanopartides exhibit quantized charging behaviors in aqueous solution. Possible mechanism for such behaviors was proposed.

Preparation and nonlinear optical properties of ultrathin composite films containing both a polyoxometalate anion and a binuclear phthalocyanine

An ultrathin composite film containing both polyoxometalate anion [PMo12O40](3-) ( PMo12) and a planar binuclear phthalocyanine, bi-CoPc, has been prepared by the electrostatic layer-by-layer self-assembly method. UV-vis measurements revealed regular film growth with each four-layer {PMo12/bi-CoPc/PSS/PAH} adsorption. The lm structure was characterized by small-angle X-ray reflectivity measurements, X-ray photoelectron spectra, and AFM images. The nanothick film shows a third-order nonlinear optical response of chi((3)) = 4.21 x 10(-12) esu. Experimental investigations also indicate that the combination of polyoxometalate anions [PMo12O40](3-) with the phthalocyanine bi-CoPc in multilayer films can enhance the third-order NLO susceptibility and modify the third-order NLO absorption of bi-CoPc.