Covalent Template-Directed Synthesis of a Spoked 18-Porphyrin Nanoring**

Majewski, Marcin A.; Stawski, Wojciech; Van Raden, Jeff; Clarke, Michael; Hart, Jack; O'Shea, James; Saywell, Alex; Anderson, Harry L.

Abstract

Rings of porphyrins mimic natural light-harvesting chlorophyll arrays and offer insights into electronic delocalization, providing a motivation for creating larger nanorings with closely spaced porphyrin units. Here, we demonstrate the first synthesis of a macrocycle consisting entirely of 5,15-linked porphyrins. This porphyrin octadecamer was constructed using a covalent six-armed template, made by cobalt-catalyzed cyclotrimerization of an H-shaped tolan with porphyrin trimer ends. The porphyrins around the circumference of the nanoring were linked together by intramolecular oxidative meso-meso coupling and partial β-β fusion, to give a nanoring consisting of six edge-fused zinc(II) porphyrin dimer units and six un-fused nickel(II) porphyrins. STM imaging on a gold surface confirms the size and shape of the spoked 18-porphyrin nanoring (calculated diameter: 4.7 nm).

• Journal Article Type: Article
• Acceptance Date: Mar 6, 2023
• Online Publication Date: Mar 24, 2023
• Publication Date: Mar 24, 2023
• Deposit Date: Mar 31, 2023
• Publicly Available Date: Mar 31, 2023
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Article Number: 202302114
• DOI: https://doi.org/10.1002/anie.202302114
• Keywords: Oxidative coupling, nanoring, porphyrin, template, aromatic compounds
• Public URL: https://nottingham-repository.worktribe.com/output/18804676
• Publisher URL: https://onlinelibrary.wiley.com/doi/10.1002/anie.202302114
• Additional Information: Received: 2023-02-11; Published: 2023-03-24