Combination of Resonance and Non-Resonance Chiral Raman Scattering in a Cobalt(III) Complex

0576140 - ÚOCHB 2024 RIV DE eng J - Journal Article
Yang, Qin - Bloino, J. - Šestáková, Hana - Šebestík, Jaroslav - Kessler, Jiří - Hudecová, J. - Kapitán, J. - Bouř, Petr
Combination of Resonance and Non-Resonance Chiral Raman Scattering in a Cobalt(III) Complex.
Angewandte Chemie - International Edition. Roč. 62, č. 45 (2023), č. článku e202312521. ISSN 1433-7851. E-ISSN 1521-3773
R&D Projects: GA ČR(CZ) GA22-04669S
Institutional support: RVO:61388963
Keywords : density functional theory * metal complexes * Raman optical activity * resonance * vibronic theory
OECD category: Physical chemistry
Impact factor: 16.6, year: 2022
Method of publishing: Open access
https://doi.org/10.1002/anie.202312521

Resonance Raman optical activity (RROA) spectra with high sensitivity reveal details on molecular structure, chirality, and excited electronic properties. Despite the difficulty of the measurements, the recorded data for the Co(III) complex with S,S-N,N-ethylenediaminedisuccinic acid are of exceptional quality and, coupled with the theory, spectacularly document the molecular behavior in resonance. This includes a huge enhancement of the chiral scattering, contribution of the antisymmetric polarizabilities to the signal, and the Herzberg-Teller effect significantly shaping the spectra. The chiral component is by about one order of magnitude bigger than for an analogous aluminum complex. The band assignment and intensity profile were confirmed by simulations based on density functional and vibronic theories. The resonance was attributed to the S0→S3 transition, with the strongest signal enhancement of Raman and ROA spectral bands below about 800 cm−1. For higher wavenumbers, other excited electronic states contribute to the scattering in a less resonant way. RROA spectroscopy thus appears as a unique tool to study the structure and electronic states of absorbing molecules in analytical chemistry, biology, and material science.
Permanent Link: https://hdl.handle.net/11104/0345732