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Wei‐Ling Wang Jian‐Wei Xu Yee‐Hing Lai 《Journal of polymer science. Part A, Polymer chemistry》2006,44(13):4154-4164
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 相似文献
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K. C. Nicolaou Dionisios Vourloumis Tianhu Li Joaquin Pastor Nicolas Winssinger Yun He Sacha Ninkovic Francisco Sarabia Hans Vallberg Frank Roschangar N. Paul King M. Ray V. Finlay Pareskevi Giannakakou Pascal Verdier-Pinard Ernest Hamel 《Angewandte Chemie (International ed. in English)》1997,36(19):2097-2103
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Hans -Peter Deutsch 《Journal of statistical physics》1992,67(5-6):1039-1082
A complete outline is given for how to determine the critical properties of polymer mixtures with extrapolation methods similar to the Ferrenberg-Swendsen techniques recently devised for spin systems. By measuring not only averages but the whole distribution of the quantities of interest, it is possible to extrapolate the data obtained in only a few simulations nearT
c
over the entire critical region, thereby saving at least 90% of the computer time normally needed to locate susceptibility peaks or cumulant intersections and still getting more precise results. A complete picture of the critical properties of polymer mixtures in the thermodynamic limit is then obtained with finite-size scaling functions. Since the amount of information extracted from a simulation in this way is drastically increased as compared to conventional methods, the investigation of mixtures with long chains or built-in asymmetries is now possible. As an example, the critical points, exponents, and amplitudes of dense, symmetric polymer mixtures with chain lengths ranging fromN=16 up toN=256 are determined within the framework of the 3D bond fluctuation model using grand canonical simulation techniques. As an example for an asymmetry, the generalization of the method to asymmetric monomer potentials is briefly discussed. 相似文献
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Marie‐France Llauro Julien Loiseau Fernande Boisson Frdric Delolme Catherine Ladavire J. Claverie 《Journal of polymer science. Part A, Polymer chemistry》2004,42(21):5439-5462
Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004 相似文献