Macrocycle-Based Covalent Organic Frameworks for Photocatalysis

¹ School of Sciences, Woxen University, Hyderabad, Telangana, India, 502345
² Department of Chemistry, VNR Viganana Jyothi Institute of Engineering and Technology, Bachupally, Hyderabad, India, 500118

Published online: 19 June 2026

Abstract

Macrocycle-based covalent organic frameworks (COFs) represent a rapidly emerging platform for photocatalysis, integrating the structural designability and porosity of COFs with the photophysical capabilities of macrocyclic compounds. This proceeding examines the integration of diverse macrocycles - including porphyrins, crown ethers, pillararenes, calix[n]arenes, and cyclodextrins - into COF architectures and their impact on photocatalytic hydrogen evolution, CO₂ reduction, H₂O₂ synthesis, and selective organic transformations. Key design strategies including bonding chemistry, structural isomerism, local electric field engineering, and heterostructure formation are discussed alongside current challenges and future perspectives. The latest, macrocycle-based COF photocatalysts have achieved exceptional performances, with 390.68 mmol g⁻¹ h⁻¹ rate of hydrogen evolution and 3324 μmol g⁻¹ h⁻¹ of H₂O₂ production. The coming together of organic chemistry, materials science, photochemistry, and computational modelling is identified as important for achieving next-generation breakthroughs.