Conjugated Macrocycle Polymer Nanoparticles with Alternating Pillarenes and Porphyrins as Struts and Cyclic Nodes

Abstract

Conjugated macrocycle polymers (CMPs) integrated using the macrocyclic confinement effect make imposing restrictions feasible on the growth of metal nanoparticles with confined size and high dispersion. For a proof-of-concept exploration, a novel nanoscale CMP is reported, denoted as DMP[5]-TPP-CMP, comprising two representative types of macrocyclic compounds, i.e., pillararene and porphyrin, as alternating strut/node components in the skeleton. With abundant anchoring sites, CMP implanted with Pd nanoparticles (Pd@DMP[5]-TPP-CMP, Pd@CMP for short) is successfully obtained through a simple post-treatment, exhibiting remarkable catalytic activity in Suzuki-Miyaura coupling (SMC) and nitrophenol reduction. The as-prepared Pd@CMP material shows favorable performance in expediting the process of SMC with an appreciable yield even under mild conditions, as well as in facilitating the electron transfer process from borohydride to nitrophenol through metal-hydride complex to produce aminophenol with a very short transformation time of 3 min and superior apparent kinetic rate constant k _app of 1.9 × 10^-2 s^-1 , higher than most palladium supports. Significantly, this multifunctional Pd@CMP composite material not only enriches the family of CMPs, but also sheds light on the development of green catalysts with excellent stability and easy recyclability without deactivation.

Keywords: conjugated polymer; functional materials; heterogenous catalyst; nanoparticles; supramolecular chemistry.