A series of new cyclopalladated arylimine compounds (3a, 3b, 3c, 4a, 4b, 4c) were synthesized and characterized. Their catalytic properties for Heck and Suzuki coupling reactions in a homogeneous system were preliminarily investigated using water as solvent, in which no ligands, air isolation or assistant solvents were needed in cross-coupling reactions. The optimization of the homogeneous system provided a basis for research on the heterogeneous catalytic reaction catalyzed by ordered self-assembly films. Organized monolayers of 3a, 3b, 3c were prepared and utilized as CC coupling catalysts. Monolayers of 3a, 3b, 3c were deposited using Langmuir–Blodgett techniques and analyzed using π–A isotherms, UV–visible and X-ray photoelectron spectroscopies and atomic force microscopy, which showed near orientation on the surface and stability under the optimized experimental conditions suitable for exploring Heck and Suzuki coupling reactions. The activity of immobilized 3c monolayer is enhanced relative to homogeneous reaction, in which the ordered monolayers are efficient with a catalyst loading as low as 10⁻⁵ mol%, turnover number as high as 79 200 and turnover frequency as high as 2640 h⁻¹. The catalytic efficiency is 100 times higher than that in the homogeneous case using the same amount and ratio of reagent. The increased activity of immobilized 3c monolayer is due to a combination of its structure and changes in conformation when deposited onto the substrate. The topographic changes of catalyst films, stability of films and catalytic activity were investigated with atomic force microscopy, cyclic voltammetry, X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectrometry, from which a heterogeneous catalytic mechanism for Suzuki coupling reaction is proposed. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems. Copyright © 2016 John Wiley & Sons, Ltd.

A series of cyclopalladated arylimine self-assembly films were prepared through chemical grafting to substrates and used to catalyze a Suzuki coupling reaction. Atomic force microscopy, water contact angle analysis, cyclic voltammetry, scanning electron microscopy, attenuated total-reflectance infrared, and X-ray photoelectron spectroscopy were used to analyze the morphology and composition of the heterogeneous catalysts. The results show that these cyclopalladated arylimine self-assembly films immobilized on substrates could be used as efficient and reusable heterogeneous catalysts in the Suzuki reaction of aryl bromides under open air conditions in aqueous solution. These catalysts exhibited 10 times the catalytic performance of the homogeneous counterpart. The palladium catalysts were grafted onto the internal surface of the round-bottomed flasks. The reaction flasks acted as both reaction vessels and catalysts, which simplified the reaction operations. The catalysts were run over 8 cycles without showing any sign of deactivation, suggesting the potential of the catalysts as advanced functional materials with applications in the heterogeneous catalysis of Suzuki reactions.

A new series of copolymer poly(N-hexadecylmethacrylamide-co-dinaphthalen-2-yl 2-allylmalonate) poly(HDMA-co-DNAM)s containing swallow-tailed double naphthyl groups and long alkyl group were designed and synthesized. The behavior of copolymer molecular arranging on water surface, patterning properties of copolymer LB films, and photochemical reactions in ultrathin film were investigated. The poly(HDMA-co-DNAM)s could form a stable, well-defined molecular orientation Langmuir monolayer at air/water interface. The polymer main chain was lying flat on water surface and the side chains attached to the main chain stretching out at the angle of about 50°. The results obtained showed that a well-ordered layer-by-layer structure was successfully controlled in LB films, in which most of naphthyl groups in poly(HDMA-co-DNAM)s LB films were in dimer and the copolymer LB films were decomposed hardly upon irradiation of deep UV light. We found that the exposed and unexposed regions of the poly(HDMA-co-DNAM)s copolymer LB films had solubility differentiation in gold etchant, which is a mixed solution of I₂/NH₄I/C₂H₅OH/H₂O. Therefore, we could obtain gold photopattern with the maximal resolution of the employed mask without any development process. Copyright © 2011 John Wiley & Sons, Ltd.

A new series of copolymer poly(N-hexadecylmeth acrylamide-co-bis(anthracen-9-ylmethyl) 2-allylmalonate) [poly(HDMA-co-DAnMAMA)]s containing swallow-tailed double anthracenyl groups and long alkyl group are designed and synthesized. The main route of the photochemical reaction of the p(HDMA-DAnMAMA)copolymer Langmuir–Blodgett (LB) films is dimerization reaction between the anthracenyl groups under the irradiation of both 365 and 248 nm for limiting irradiation time, resulting to a fine negative-tone pattern. On the other hand, the anthracenyl groups act just as photodecomposition group under 248 nm for longer irradiation time, resulting to a fine positive-tone pattern. Consequently, positive-tone and negative-tone pattern are obtained by choosing not only a suitable irradiation light wavelength, but the irradiation time at 248 nm. Moreover, it is found that the exposed and unexposed regions of copolymer LB films irradiated at 248 nm have solubility differentiation in gold etchant (I₂/NH₄I/C₂H₅OH/H₂O), that is to say, the gold photopatterns with the maximal resolution of the used mask can be obtained easily without any development process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 139–147, 2012