Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 39, Pages 21205-21210Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202107600
Keywords
chirality; electronic circular dichroism; Raman scattering; resonance Raman optical activity; vitamin B-12
Categories
Funding
- National Science Centre Poland [2019/35/B/ST4/04161, 2019/33/N/ST4/01986]
- Foundation for Polish Sciences [FNP TEAM POIR.04.04.00-00-4232/17-00]
- Ministry of Education [CZ.02.1.01/0.0/0.0/16019/0000729, CZ.02.2.69/0.0/0.0/18053/0016940]
- Science Foundation of the Czech Republic [20-10144S]
- PL-Grid Infrastructure
- Polish National Agency for Academic Exchange [PPN/BCZ/2019/1/00058/U/00001]
- Priority Research Area BioS under the program Excellence Initiative-Research University at the Jagiellonian University in Krakow
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Resonance Raman optical activity (RROA) is a sensitive tool for molecular detection, but its measurement poses challenges. Reliable recording of RROA for chiral colorful compounds requires consideration of the effect of electronic circular dichroism (ECD) on ROA spectra. Neglecting the ECD effect can lead to misinterpretation of recorded spectra and erroneous conclusions about molecular structure.
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.
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