Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

Kinetic behaviour of aluminum naphthenate/benzene system in process of gelation and degradation

The kinetic behaviour of aluminum naphthenate/benzene system in the process of gelation and degradation was systematically studied. The results obtained from the kinetic experiments indicated that the gelation stage was in accordance with a kinetic model of an auto-catalytic first-order reaction, and the degradation stage was a simple first-order reaction. The rate constants in these two stages at various temperaturs were measured. And the determined apparent activation energies for the gelation stage and for the degradation stage are 27.5±2.0 and 37.7±2.3 kJ/mol, respectively.     

On the persistence of elliptic lower-dimensional tori in Hamiltonian systems under the first Melnikov condition and Rüssmann’s non-degeneracy condition

In this paper we formulate a theorem on the persistence of elliptic lower-dimensional invariant tori for nearly integrable analytic Hamiltonian systems under the first Melnikov condition and Rüssmann’s non-degeneracy condition, and give the measure estimates of parameters for the non-resonance conditions under Rüssmann’s non-degeneracy condition, which is essential for the proof of our result.     

Stagnation flow on a cylinder with partial slip--an exact solution of the Navier-Stokes equations

The stagnation slip flow on an axially moving cylinder is studied.The Navier–Stokes and energy equations reduce to nonlinearordinary differential equations under a similarity transform.For large slip, the flow field decays exponentially into potentialflow. The heat transfer can be expressed as an incomplete gammafunction. In general, the heat transfer increases with slip,Prandtl number and Reynolds number.     

Studies on the method of total synthesis of koumine: I. 4-Substituted 1,2-dihydropyridine derivatives and their function as a conjugated diene in Diels-Alder reaction

A route to the total synthesis of koumine has been suggested. Five 4-substituted 1, 2-d hydropyridine derivatives, which are supposed to be a conjugated diene of Diels-Alder reaction to produce the isoquinuclidine ring of koumine, have been synthesized. Only two of them were found to be able to undergo the Diels-Alder reaction. The stereochemistry of the reaction product has also been examined.     

Anchoring Properties of Nematic Liquid Crystals Studied Using the Attenuated Total Reflection Method

By using the attenuated total reflection method associated with the excitation of surface plasmons, the tilt angle of the liquid crystal director and its gradient at the surface are measured in a planar nematic cell as a function of the applied voltage. The surface anchoring anisotropy δπ of the liquid crystal and the surface elastic constant k_s, are found to be δπ = 0.288 erg/cm and k_s, = 9·12 × 10^-11 erg, respectively, when the boundary condition suggested by Barbero et al is used. The theoretical and experimental values obtained with this boundary condition and that of Mada are discussed. The results show that the boundary condition proposed by Barbero et al is in better agreement with the experiment.     

Bipyridinophane‐containing conjugated polymers modulated with an intramolecular aromatic C?H/π interaction

Bipyridinophane–fluorene conjugated copolymers have been synthesized via Suzuki and Heck coupling reactions from 5,8‐dibromo‐2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane and suitable fluorene precursors. Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P7 ) exhibits large absorption and emission redshifts of 20 and 34 nm, respectively, with respect to its planar reference polymer Poly[2,7‐(9,9‐dihexylfluorene)‐co‐alt‐1,4‐(2,5‐dimethylbenzene)] ( P11 ), which bears the same polymer backbone as P7 . These spectral shifts originate from intramolecular aromatic C? H/π interactions, which are evidenced by ultraviolet–visible and ¹H NMR spectra as well as X‐ray single‐crystal structural analysis. However, the effect of the intramolecular aromatic C? H/π interactions on the spectral shift in poly[9,9‐dihexylfluorene‐2,7‐yleneethynylene‐co‐alt‐5,8‐(2,11‐dithia[3]paracyclo[3](4,4′)‐2,2′‐bipyridinophane)] ( P10 ) is much weaker. Most interestingly, the quenching behaviors of these two conjugated polymers are largely dependent on the polymer backbone. For example, the fluorescence of P7 is efficiently quenched by Cu²⁺, Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, and Ag⁺ ions. In contrast, only Cu²⁺, Co²⁺, and Ni²⁺ ions can partially quench the fluorescence of P10 , but much less efficiently than the fluorescence of P7 . The static Stern–Volmer quenching constants of Cu²⁺, Co²⁺, and Ni²⁺ ions toward P7 are of the order of 10⁶ M^?1, being 1300, 2500, and 37,300 times larger than those of P10 , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4154–4164, 2006     

VO2-Based Infrared Microbolometer Array

V0₂-based thin film materials on silicon substrates are fabricated by ion beam sputtering and a post-annealing which is different from the conventional fabricating method. An infrared linear microbolometer array with 128 pixels is prepared using as-deposited vanadium dioxide thin films. Optical and electrical properties for V0₂-based microbolometer array are tested.     

Glass transitions in hydrogen-bonded polymer complexes

Mutual precipitates of poly (N, N-dimethyl acrylamide) and poly (4-hydroxystyrene) were collected from dioxane, methanol, or acetone. The glass transition (T_g) temperatures of the precipitates are higher than the weight-average values. Clear films cast from dimethylformamide solutions have lower T_g values. Complexation also occurred between poly (ethyl oxazoline) and poly (4-hydroxystyrene) in dioxane and between poly (vinyl pyrrolidone) and poly (4-hydroxystyrene) in methanol. Again, the glass transition temperatures of the precipitates are higher than the values for the blend films. The ΔC_p values associated with the glass transitions of the complexes are smaller than those of the blends having the same compositions. Negative excess heat capacities of mixing have been observed for several precipitates.