Vibrational Circular Dichroism of a Chiral Triplet Nitrene Investigated Under Matrix‐Isolation Conditions in Parahydrogen

• Published in: Chemistry : a European journal Vol. 30; no. 40; pp. e202401731 - n/a
• Main Authors: Beyer, Frederike, Grassin, Corentin, Rowen, Julien F., Sander, Wolfram, Merten, Christian
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 16-07-2024
• Subjects: Chirality; Circular dichroism; Dichroism; Feasibility studies; Matrix isolation; Photochemicals; Reactive intermediates; Spectra; Vibrational analysis; Matrix isolation; Vibrational analysis; Reactive intermediates; Chirality; Circular dichroism
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202401731

Vibrational circular dichroism (VCD) spectra of chiral high‐spin organic radicals are expected to show a strong intensity enhancement and are thought to be difficult to predict using state‐of‐the‐art theoretical methods. Herein we show that the chiral triplet nitrene obtained from photochemical cleavage of N2 from enantiopure 2‐azido‐9H‐fluorenol does not feature extraordinarily strong intensities and that the experimental spectra match nicely with calculated ones. Thereby, this study demonstrates the general feasibility of studies on chiral high‐spin organics by matrix‐isolation VCD.
A chiral triplet nitrene was photochemically generated from the parent azide compound and characterized by means of matrix‐isolation vibrational circular dichroism (VCD) spectroscopy. Despite the high‐spin nature of the target compound, no intensity enhancement was observed, and we show that matrix‐isolation VCD spectra of high‐spin organic radicals can indeed be computed.