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

• Published in: Small (Weinheim an der Bergstrasse, Germany) Vol. 15; no. 12; pp. e1805509 - n/a
• Main Authors: Li, Zheng, Li, Xi, Yang, Ying‐Wei
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.03.2019
• Subjects: Aminophenol; Anchoring; Catalysis; Catalytic activity; Composite materials; conjugated polymer; Coordination compounds; Deactivation; Electron transfer; functional materials; heterogenous catalyst; Macrocyclic compounds; Nanoparticles; Nanotechnology; Nitrophenol; Palladium; Porphyrins; Recyclability; Struts; supramolecular chemistry; Sustainable development; nanoparticles; heterogenous catalyst; functional materials; conjugated polymer; supramolecular chemistry
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.201805509

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. Conjugated macrocycle polymer nanoparticles consisting of dual macrocyclic compounds (pillarene and porphyrin) as alternating strut/node components in the skeleton are first prepared, followed by the immobilization of Pd nanoparticles via a simple post‐treatment method. The resulting composite nanomaterials exhibit excellent stability, remarkable catalytic activity, and easy recyclability in Suzuki–Miyaura coupling and nitrophenol reduction.