Disentangling global and local ring currents

Bradley, D., Jirasek, M., Anderson, H. L. and Peeks, M. D. (2023) Disentangling global and local ring currents. Chemical Science, 14(7), pp. 1762-1768. (doi: 10.1039/D2SC05923A) (PMID:36819862) (PMCID:PMC9930925)

Abstract

Magnetic field-induced ring currents in aromatic and antiaromatic molecules cause characteristic shielding and deshielding effects in the molecules' NMR spectra. However, it is difficult to analyze (anti)aromaticity directly from experimental NMR data if a molecule has multiple ring current pathways. Here we present a method for using the Biot-Savart law to deconvolute the contributions of different ring currents to the experimental NMR spectra of polycyclic compounds. This method accurately quantifies local and global ring current susceptibilities in porphyrin nanorings, as well as in a bicyclic dithienothiophene-bridged [34]octaphyrin. There is excellent agreement between ring current susceptibilities derived from both experimental and computationally-predicted chemical shifts, and with ring currents calculated by the GIMIC method. Our method can be applied to any polycyclic system, with any number of ring currents, provided that appropriate NMR data are available.

• Item Type: Articles
• Additional Information: This project was undertaken using resources and services from the National Computational Infrastructure (NCI), which is supported by the Australian Government. UNSW provided support in the form of a Scientia Lectureship (M. D. P.) and PhD scholarship (D. B.). H. L. A. acknowledges the ERC (Advanced Grants 320969 and 885606).
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Jirasek, Dr Michael

Creator Roles

Jirasek, M.: Methodology, Software, Investigation, Writing – review and editing

• Authors: Bradley, D., Jirasek, M., Anderson, H. L., and Peeks, M. D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Chemical Science
• Publisher: The Royal Society of Chemistry
• ISSN: 2041-6539
• ISSN (Online): 2041-6539
• Published Online: 16 January 2023
• Copyright Holders: Copyright © 2023 The Authors
• First Published: First published in Chemical Science 14(7): 1762-1768
• Publisher Policy: Reproduced under a Creative Commons License