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Recognition of the True and False Resonance Raman Optical Activity
Author(s) -
Machalska Ewa,
Zajac Grzegorz,
Wierzba Aleksandra J.,
Kapitán Josef,
Andruniów Tadeusz,
Spiegel Maciej,
Gryko Dorota,
Bouř Petr,
Baranska Malgorzata
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202107600
Subject(s) - raman optical activity , raman spectroscopy , chemistry , spectral line , circular dichroism , resonance (particle physics) , density functional theory , analytical chemistry (journal) , time dependent density functional theory , derivative (finance) , nuclear magnetic resonance , molecular physics , computational chemistry , optics , crystallography , chromatography , atomic physics , physics , astronomy , financial economics , economics
Resonance Raman optical activity (RROA) possesses all aspects of a sensitive tool for molecular detection, but its measurement remains challenging. We demonstrate that reliable recording of RROA of chiral colorful compounds is possible, but only after considering the effect of the electronic circular dichroism (ECD) on the ROA spectra induced by the dissolved chiral compound. We show RROA for a number of model vitamin B 12 derivatives that are chemically similar but exhibit distinctively different spectroscopic behavior. The ECD/ROA effect is proportional to the concentration and dependent on the optical pathlength of the light propagating through the sample. It can severely alter relative band intensities and signs in the natural RROA spectra. The spectra analyses are supported by computational modeling based on density functional theory. Neglecting the ECD effect during ROA measurement can lead to misinterpretation of the recorded spectra and erroneous conclusions about the molecular structure.