Supramolecular Near‐Infrared Photocatalysts for Efficient and Oxygen‐Tolerant Aqueous RAFT Polymerization
Abstract
ABSTRACT Near‐infrared (NIR) photocontrolled polymerization in aqueous media is promising for bioapplications. However, it typically suffers from low polymerization efficiency and requires high catalyst loadings due to the aggregated nature of the photocatalyst. Herein, we report a supramolecular strategy to overcome this limitation via host–guest complexation between an anionic photocatalyst and a cationic macrocycle. Spectroscopic and computational studies confirmed the formation of stable 1:1 host–guest complexes via synergistic electrostatic, π‐π, and hydrophobic interactions. Supramolecular complexation effectively suppresses photocatalyst aggregation and significantly enhances oxygen tolerance and reaction kinetics, enabling high‐throughput, open‐to‐air NIR‐mediated reversible addition‐fragmentation chain‐transfer (RAFT) polymerizations to be conducted in aqueous media with excellent control over molecular weight and dispersity. High conversions and low dispersities were achieved even for polymerizations conducted through thick porcine tissue barriers, demonstrating excellent NIR penetration depth. This work provides a versatile supramolecular approach to enhancing photocatalyst performance, highlighting new avenues for precision polymer synthesis under biologically relevant conditions.
Article Details
Authors (7)
Siyan Guan
State Key Laboratory of Supramolecular Structure and Materials College of Chemistry Jilin University Changchun China
Yue‐Yi Zhang
Academy of Interdisciplinary Studies on Intelligent Molecules Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin China
Shudi Zhang
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry
Zhi‐Yuan Zhang
Academy of Interdisciplinary Studies on Intelligent Molecules Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry Tianjin Normal University Tianjin China
Steven P. Armes
School of Mathematical and Physical Sciences, University of Sheffield, Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
Chunju Li
Academy of Interdisciplinary Studies on Intelligent Molecules, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry
Zesheng An
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry