Phase Behaviors and Photoresponsive Thin Films of Syndiotactic Side-Chain Liquid Crystalline Polymers with High Densely Substituted Azobenzene Mesogens.

Azobenzene-containing polymers (azopolymers) are a kind of fascinating stimuli-responsive materials with broad and versatile applications. In this work, a series of syndiotactic C1 type azopolymers of Pm-Azo-Cn with side-chain azobenzene mesogens of varied length alkoxy tails (n=1, 4, 8, 10) and different length alkyl spacers (m=6, 10) have been prepared via Rh-catalyzed carbene polymerization. The thermal properties and ordered assembly structures of thus synthesized side chain liquid crystalline polymers (SCLCPs) have been systematically investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM) and variable-temperature small/wide-angle X-ray scattering (SAXS/WAXS) analyses. P10-Azo-C1 and P10-Azo-C4 with shorter alkoxy tails exhibited hierarchical structures SmB/Colob and transformed into SmA/Colob at a higher temperature, while P10-Azo-C8 and P10-Azo-C10 with longer alkoxy tails only displayed side group dominated layered SmB phase and transformed into SmA phase at higher temperatures. For P6-Azo-C4 with a shorter spacer only showed a less ordered SmA phase owing to interference by partly coupling between the side chain azobenzene mesogens and the helical backbone. More importantly, the series high densely substituted syndiotactic C1 azopolymer thin films, exhibited evidently and smoothly reversible photoresponsive properties, which demonstrated promising photoresponsive device applications.

Mechanochemical Rhodium-Catalyzed C-H Bond Amidation of Ferrocenes by Ball Milling.

A direct protocol for Rh-catalyzed C-H amidation of ferrocenes in a ball mill using dioxazolones as the amide source under solvent-free conditions was developed. The corresponding ortho-aminated products were formed in 3 hours and the yields were up to 99% in the absence of base. This method could be a typically sustainable and environmental-friendly alternative method to traditional methodologies, with the advantages of wide substrate range, good functional group tolerance and gram-scale synthesis.

Strategies towards potent trypanocidal drugs: Application of Rh-catalyzed [2 + 2 + 2] cycloadditions, sulfonyl phthalide annulation and nitroalkene reactions for the synthesis of substituted quinones and their evaluation against Trypanosoma cruzi.

Rhodium-catalyzed [2 + 2 + 2] cycloadditions, sulfonyl phthalide annulations and nitroalkene reactions have been employed for the synthesis of 56 quinone-based compounds. These were evaluated against Trypanosoma cruzi, the parasite that causes Chagas disease. The reactions described here are part of a program that aims to utilize modern, versatile and efficient synthetic methods for the one or two step preparation of trypanocidal compounds. We have identified 9 compounds with potent activity against the parasite; 3 of these were 30-fold more potent than benznidazole (Bz), a drug used for the treatment of Chagas disease. This article provides a comprehensive outline of reactions involving over 120 compounds aimed at the discovery of new quinone-based frameworks with activity against T. cruzi.

Rhodium-Catalyzed Asymmetric 1,4-Additions, in Water at Room Temperature, with In-Flask Catalyst Recycling.

Using the newly introduced designer surfactant polyethyleneglycol ubiquinol sebacate (PQS), as the platform for micellar catalysis, nonracemic BINAP has been covalently attached and rhodium(I) inserted to form PQS-BINAP-Rh. This species, the first example of a nonracemically-ligated transition metal catalyst-tethered amphiphile, can be utilized for Rh-catalyzed asymmetric conjugate addition reactions of arylboronic acids to acyclic and cyclic enones. These are performed in water at room temperature, while the catalyst can be recycled without its removal from water in the reaction vessel.