Ring-Opening Polymerization of Trimethylene Carbonate with Phosphazene Organocatalyst.

Aliphatic polycarbonate (APC) compounds are an important class of biodegradable materials with excellent biocompatibility, good biodegradability, and low toxicity, and the study of these compounds and their modification products aims to obtain biodegradable materials with better performance. In this context, the ring-opening polymerization (ROP) of trimethylene carbonate (TMC) from a low nucleophilic organic superbase of phosphazene (t-BuP4) as a catalyst and benzyl alcohol (BnOH) as an initiator at room temperature was carefully studied to prepare poly(trimethylene carbonate) (PTMC) which is one of the most studied APC. 1H NMR and SEC measurements clearly demonstrate the presence of a benzyloxy group at the α-terminus of the obtained PTMC homopolymers while investigation of the polymerization kinetics confirms the controlled/living nature of t-BuP4-catalyzed ROP of TMC. On the basis of this, the block copolymerization of TMC and δ-valerolactone (VL)/ε-caprolactone (CL) was successfully carried out to give PTMC-b-PCL and PTMC-b-PVL copolymers. Furthermore, PTMC with terminal functionality was also prepared with the organocatalytic ROP of TMC through functional initiators. We believe that the present ROP system is a robust, highly efficient, and practical strategy for producing excellent biocompatible and biodegradable PTMC-based materials.

Controlling Charge Transport in Molecular Wires through Transannular π-π Interaction.

This paper describes the influence of the transannular π-π interaction in controlling the carrier transport in molecular wires by employing the STM break junction technique. Five pentaphenylene-based molecular wires that contained [2.2]paracyclophane-1,9-dienes (PCD) as the building block were prepared as model compounds. Functional substituents with different electronic properties, ranging from strong acceptors to strong donors, were attached to the top parallel aromatic ring and used as a gate. It was found that the carrier transport features of these molecular wires, such as single-molecule conductance and a charge-tunneling barrier, can be systematically controlled through the transannular π-π interaction.