Organolanthanides with 3-(2-pyridylmethyl) indenyl ligands: synthesis, crystal structures and catalytic activities of divalent complexes for epsilon-caprolactone polymerization

Reaction of 3-(2-pyridylmethyl)indenyl lithium (1) with LnI(2)(THF)(2) (Ln = Sm, Yb) in THF produced the divalent organolanthanides (C5H4NCH2C9H6)(2)Ln(II)(THF) (Ln = Sm (2), Yb (3)) in high yield. 1 reacts with LnCl(3) (Ln = Nd, Sm, Yb) in THF to give bis(3-(2-pyridylmethyl)indenyl) lanthanide chlorides (C5H4NCH2C9H6)(2)Ln(III)Cl (Ln = Nd (4), Sm (5)) and the unexpected divalent lanthanides 3 (Ln = Yb). Complexes 2-5 show more stable in air than the non-functionalized analogues. X-ray structural analyses of 2-4 were performed. 2 and 3 belong to the high symmetrical space group (Cmcm) with the same structures, they are THF-solvated 9-coordinate monomeric in the solid state, while 4 is an unsolvated 9-coordinate monomer with a trans arrangement of both the side-arms and indenyl rings in the solid state. Additionally, 2 and 3 show moderate polymerization activities for F-caprolactone (CL).

Syntheses and crystal structures of bis(tetrahydrofurfurylindenyl) lanthanocene chlorides (C4H7OCH2C9H6)(2)LnCl (Ln = La, Lu)

Reaction of two equivalents of tetrahydrofurfuryl indenyl lithium with anhydrous lanthanide trichlorides in THF afforded bis(tetrahydrofurfurylindenyl) lanthanide chlorides (C4H7OCH2C9H6)(2)LnCl, Ln=La(l), Pr(2), Lu(3). Complexes I and 3 are characterized by single-crystal analysis. The results of crystal structural determination reveal that they are 9-coordinate monomeric intramolecular complexes with a trans arrangement of both the sidearms and indenyl rings in the solid state. The effects of rare earth ionic radii on the structures Of (C4H7OCH2C9H6)(2)LnCl are discussed.

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

Syntheses, crystal structures and properties of two Cu(II) coordination polymers: Cu(C3N2H4)(2)(HL)(2) andCU(C3N2H4)(2)L with C3N2H4 = imidazole, H2L = adipic acid

The reactions of freshly prepared Cu(OH)(2).xH(2)O and Cu(OH)(2-2y)(CO3)(y).zH(2)O precipitates with imidazole and adipic acid in CH3OH/H2O at pH = 5.4 yielded CU(C3N2H4)(2)(HL)(2) 1 and CU(C3N2H4)(2)L 2, respectively. Complex 1 consists of ribbon-like polymeric chains (1)(infinity)[CU(C3N2H4)(2)(HL)(4/2)], in which the octahedrally coordinated Cu atoms are doubly bridged by bis-monodentate hydrogen adipato ligands. The interchain N-H...O hydrogen bonding interactions are responsible for supramolecular assembly of the polymeric chains into open 3D frameworks and two-fold interpenetration of the resulting open frameworks completes the crystal structure of 1. Within complex 2, the Cu atoms are penta-coordinated to form CuN2O3 square pyramids and condensed into CU2N4O4 dimers, which are doubly bridged by twisted bis-monodentate adipato ligands into polymeric chains (1)(infinity)([CU(C3N2H4)(2)](2)L-4/2) with 4- and 18-membered rings progressing alternatively. The polymeric chains are assembled due to interchain N-H...O hydrogen bonding interactions. The thermal and magnetic behaviors of 1 and 2 is discussed.

Direct electrochemical generation of conducting polymer micro-rings

Self-doped polyaniline (PANI) micro-rings have been successfully generated electrochemically. The polymer forming rings were about 100 nm wide, and the ring diameter is tunable from several to dozens of micrometres depending on deferent current densities. The morphology of such nanostructured polyaniline rings was investigated and further confirmed with field-emission scanning electron microscopy (FE-SEM). Furthermore, the film was characterized using UV/visible spectroscopy and cyclic voltammetry. The bubble template formation mechanism of the micro-rings was also proposed. Such nanostructured materials synthesized electrochemically open up a new approach to surface morphology control.

Two new Cu-II coordination polymers: Studies of topological networks and water clusters

Two new Cull coordination polymers, namely [Cu-2(BDC)(2)(L)(4)(H2O)(2)]center dot 14H(2)O (1) and [Cu-1.5(BTC)(L)(1.5)(H2O)(0.5)]center dot 2H(2)O (2), where L = 1,1'-(1,4-butanediyl)bis(imidazole), BDC = 1,4-benzene dicarboxylate, and BTC = 1,3,5-benzenetricarboxylate, have been synthesized at room temperature. Complex 1 exhibits an unusual, square-planar, four-connected 2D (2)(6)4 net, which has been predicated by Wells. Interestingly, three types of water clusters, namely (H2O)(6), (H2O)(8), and (H2O)(10), are observed in the hydrogen-bonded layers constructed by the BDC ligands and water molecules. The BTC anion in compound 2 is coordinated to the Cu" cation as tetradentate ligand to form a (6(6))(2)(4(2)6(4)8(4))(2)(6(4)810) net containing three kinds of nonequivalent points, Thermogravimetric analyses (TGA) and IR spectra for 1 and 2 are also discussed in detail.

Syntheses and properties of novel polyimides derived from 2-(4-aminophenyl)-5-aminopyrimidine

2-(4-Aminophenyl)-5-aminopyrimidine (4) is synthesized via a condensation reaction of vinamidium salts and amidine chloride salts, followed by hydrazine palladium catalyzed reduction. A series of novel homo- and copolyimides containing pyrimidine unit are prepared from the diamine and 1,4-phenylenediamine (PDA) with pyromellitic dianhydride (PMDA) or 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidization method. The poly(amic acid) precursors had inherent viscosities of 0.97-4.38 dL/g (c = 0.5 g/dL, in DMAc, 30 degrees C) and all of them could be cast and thermally converted into flexible and tough polyimide films. All of the polyimides showed excellent thermal stability and mechanical properties. The glass transition temperatures of the resulting polyimides are in the range of 307-434 degrees C and the 10% weight loss temperature is in the range of 556-609 degrees C under air. The polyimide films possess strength at break in the range of 185-271 MPa, elongations at break in the range of 6.8-51%, and tensile modulus in the range of 3.5-6.46 GPa. The polymer films are insoluble in common organic solvents, exhibiting high chemical resistance.

Self-assembled monolayers of novel surface-bound dendrons: Peripheral structure determines surface organization

The synthetic and functional versatility of dendrimers and their well-defined shapes make them attractive molecules for surface modification. We synthesized six structurally very similar surface-bound dendrons and used them as building blocks for the preparation of self-assembled monolayers (SAMs) on a gold surface. We studied the effects of the surface-bound dendron's main structure, peripheral substituents, and the coadsorption process on its self-assembling behavior. Using scanning tunneling microscopy (STM), we observed nanostripes for SAMs of the surface-bound dendron consisting of symmetrical benzene rings. When we changed the symmetrical dendron's structure slightly, by increasing or decreasing the numbers of benzene rings at one wedge, we found no ordered structures were formed by the asymmetrical dendrons. We also introduced two kinds of substituents, heptane chains and oligo(ethylene oxide) chains, to the symmetrical dendron's periphery. Heptane chains appear to enhance the interaction between symmetrical backbones, leading to the formation of stripes, while oligo(ethylene oxide) chains appear to weaken the interaction between symmetrical backbones, resulting in a homogeneous structure. Dendrons with both heptane and oligo(ethylene oxide) chains exhibit nanophase separation in a confined state, leading to the formation of a honeycomb structure.

Synthesis, characterization, photoluminescent and electroluminescent properties of new conjugated 2,2 '-(arylenedivinylene)bis-8-substituted quinolines

A series of new PPV oligomers containing 8-substituted quinoline, 2,2'-(arylenedivinylene) bis-8-quinoline derivatives, were designed and synthesized via a Knoevenagel condensation reaction of quinaldine, 8-hydroxy-or 8-methoxy-quinaldine with aromatic dialdehydes. These PPV oligomers were characterized by H-1 and C-13-NMR, X-ray diffraction, elemental analysis, UV-visible and fluorescence spectroscopies. The X-ray diffraction investigation showed that there are intermolecular pi...pi interactions in the solid state in 1 and 3. The optical and photoluminescent properties study demonstrated that the emission color of the resulting materials varies from blue to yellow and is dependent on the substituents (pi-donor and pi-acceptor groups) on both sides of the conjugated molecules and the aromatic core in the middle of the conjugated backbones. The electroluminescent devices using compounds 1-4 as the emitters and electron-transporting layers were fabricated with the structure ITO/NPB/emitter/LiF/Al. The best device performance with the maximum brightness of 5530 cd m(-2) and the luminous efficiency of 2.4 cd A(-1) is achieved by using compound 4, with intramolecular charge transfer character, as the emitter; these values represent a more than 5-fold improvement in brightness and efficiency compared to compound 3 without methoxy groups on the phenyl rings.

Patterning and photolumine scent properties of perovskite-type organic/inorganic hybrid luminescent films by soft lithography

Perovskite-type organic/inorganic hybrid layered compound (C6H5C2H4NH3)(2)PbI4 was synthesized. The patterning Of (C6H5C2H4NH3)(2)PbI4 thin films on silicon substrate was realized by the micromolding in capillaries (MIMIC) process, a kind of soft lithography. Bright green luminescent stripes with different widths (50, 15, 0.8 mum) have been obtained. The structure and optical properties Of (C6H5C2H4NH3)(2)PbI4 films were characterized by X-ray diffraction (XRD), UV/Vis absorption and photoluminescence excitation and emission spectra, respectively. It is shown that the organic-inorganic layered (C6H5C2H4NH3)(2)PbI4 film was c-axis oriented, paralleling to the substrate plane. Green exciton emission at 525 nm was observed in the film, and the explanations for it were given.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

Syntheses and crystal structures of bis(tetrahydrofurfurylindenyl) lanthanocene chlorides (C4H7OCH2C9H6)(2)LnCl (Ln = Nd, Sm, Dy, Ho, Er, Yb)

Reaction of anhydrous lanthanide trichlorides with tetrahydrofurfuryl indenyl lithium in THF afforded bis(tetrahydrofurfurylindenyl) lanthanocene chlorides complexes (C4H7OCH2C9H6)(2) LnCl, Ln = Nd (1), Sm (2), Dy (3), Ho (4), Er (5), Yb (6). The X-ray crystallographic structures of all the six complexes were determined and these indicate that they are unsolvated nine-coordinate monomeric complexes with a trans arrangement of both the sidearm and indenyl rings in the solid state. They belong to the same crystal system (orthorhombic) and space group (P2(1)2(1)2(1)) with the same structure. Especially, they are more stable to air and moisture than the corresponding unsubstituted indenyl lanthanide complexes.

A study of the crystallographic equivalence of ether and ketone groups in poly(aryl ether ketone)s

Crystallographic equivalence of ether and ketone in all para-substituted PAEKs crystallized in form I was discussed in this paper. In a word, crystallographic equivalence between ether and ketone groups is tenable when polymer contains only phenyl rings in the repeat unit. If a polymer contains a diphenyl group in the repeat unit, two cases should be distinguished. In the case of PEDEKK and PEEKDK, crystallographic equivalence between ether and ketone linkages is untenable, However, in the case of PEDK and PEDEKDK, crystallographic equivalence between ether and ketone linkages is still tenable.

Investigation into self-assembled monolayers of a polyether dendron thiol: Chemisorption, kinetics, and patterned surface

Different sizes of Frechet-type dendrons with a thiol group at the focal point were synthesized, well characterized, and used as building blocks for the preparation of self-assembled monolayers (SAMs) on metal surfaces. From the studies of the kinetic process of dendron thiol self-assembling on gold, it is shown that the dendron thiol assembling proceeds with different adsorption rates depending on the assembly time. In contrast to normal alkanethiols forming highly molecular structures on metal surfaces, the SAMs of polyether dendron form patterned surfaces with nanometer-sized features and in long-range order. It is found that the patterned stripes are closely related to the size of the dendron, and the patterned stripes can be improved by thermal annealing.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.