An in situ generated cationic allylpalladium complex bearing N‐heterocyclic carbene (NHC) ligands, derived from the reaction of [(η3‐C3H5)Pd(NHC)Cl] with AgX (X = BF4 or SbF6), is an active catalyst for the addition polymerization of norbornene and norbornene derivatives [5‐norbornene‐2‐carboxylic acid methyl ester (b) and 5‐norbornene‐2‐carboxylic acid n‐butyl ester (c)] with an ester group containing a large portion of endo‐isomers. The catalytic activities, polymer yields, molecular weights, and molecular weight distributions of polynorbornenes were investigated under various reaction conditions: the catalytic activity was highly dependent on the counteranion, the reaction solvent, and the reaction temperature. For b, as the portion of an endo‐isomer increased, the activity of 13(SbF −6) was much higher than those of 14 and 15, and for c (exo/endo = 95:5), the maximum turn over number (TON) was observed with 15(SbF −6). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3042–3052, 2007

The heterometallic complex (NH(3))(2)YbFe(CO)(4) was prepared from the reduction of Fe(3)(CO)(12) by Yb in liquid ammonia. Ammonia was displaced from (NH(3))(2)YbFe(CO)(4) by acetonitrile in acetonitrile solution, and the crystalline compounds {[(CH(3)CN)(3)YbFe(CO)(4))](2).CH(3)CN}(infinity) and [(CH(3)CN)(3)YbFe(CO)(4)](infinity) were obtained. An earlier X-ray study of {[(CH(3)CN)(3)YbFe(CO)(4)](2).CH(3)CN}(infinity) showed that it is a ladder polymer with direct Yb-Fe bonds. In the present study, an X-ray crystal structure analysis also showed that [(CH(3)CN)(3)YbFe(CO)(4)](infinity) is a sheetlike array with direct Yb-Fe bonds. Crystal data for {[(CH(3)CN)(3)YbFe(CO)(4)](2).CH(3)CN}(infinity): monoclinic space group P2(1)/c, a = 21.515(8) Å, b = 7.838(2) Å, c = 19.866(6) Å, beta = 105.47(2) degrees, Z = 4. Crystal data for [(CH(3)CN)(3)YbFe(CO)(4)](infinity): monoclinic space group P2(1)/n, a = 8.364(3) Å, b = 9.605(5) Å, c = 17.240(6) Å, beta = 92.22(3) degrees, Z = 4. Electrical conductivity measurements in acetonitrile show that these acetonitrile complexes are partially dissociated into ionic species. IR and NMR spectra of the solutions reveal the presence of [HFe(CO)(4)](-). However, upon recrystallization, the acetonitrile complexes show no evidence for the presence of [HFe(CO)(4)](-) on the basis of their IR spectra. The solid state MAS (2)H NMR spectra of deuterated acetonitrile complexes give no evidence for [(2)HFe(CO)(4)](-). It appears that rupture of the Yb-Fe bond could occur in solution to generate the ion pair [L(n)Yb](2+)[Fe(CO)(4)](2-), but then the highly basic [Fe(CO)(4)](2-) anion could abstract a proton from a coordinated acetonitrile ligand to form [HFe(CO)(4)](-). However, upon crystallization, the proton could be transferred back to the ligand, which results in the neutral polymeric species.

We have successfully fabricated triacetylcellulose (TAC) polymer-silica nanocomposite films having up to 40 wt % of incorporated silica nanoparticles by deliberately designing a surface ligand that has a structure similar to that of polymer repeating units and effectively modifying the surface of silica nanoparticles through chemical bonding. Cross-sectional TEM analysis reveals no significant aggregation in all TAC-silica nanocomposite films. Thermal analysis results suggested that TAC-silica nanocomposites had higher T(g) and T(c) values as compared to pure TAC, and the increase in T(g) and T(c) was affected by the silica content. The transparency of all the nanocomposite films was over 80% in the visible range, confirming the excellent compatibility of nanoparticles with TAC. In this study, we enhance the interaction between nanoparticles and polymer matrices by modifying the surface of nanoparticles with a ligand that has a structure similar to that of polymer repeating units. It is expected that this method can be applied to other polymer systems to develop useful nanocomposites.

A new approach to the synthesis of photoactive comb-shaped homo-and copolyamides containing azobenzene, cinnamate, and coumarin side groups for photoalignment of liquid crystals was elaborated. Photooptical properties and photoorientational ability of these polymers with respect to liquid crystals were studied. It was shown that polarized UV irradiation of all spin-coated polyamides leads to orientation of liquid crystalline molecules deposited on the polyamide thin films. The synthesized polymers containing cinnamate and coumarin side groups as well as azobenzene-containing cyanoand nitro-substituted polymers demonstrated good orientation ability in relation to liquid crystals displaying photoinduced planar orientation with high dichroism values within the range of 0.68-0.72. Contrary to the above-mentioned polyamides, azobenzene-containing fluorosubstituted polymers induced a homeotropic orientation of liquid crystals. It was shown that the synthesized photoactive polyamides can be considered as promising photoalignment materials for application in display technology, photonics, and other "smart" optical devices.

No abstract