Yang Qin, Bloino Julien, Šestáková Hana, Šebestík Jaroslav, Kessler Jiří, Hudecová Jana, Kapitán Josef, Bouř Petr
Institute of Organic Chemistry and Biochemistry Academy of Sciences, Flemingovo náměstí 2, 16610, Prague, Czech Republic.
Scuola Normale Superiore di Pisa, Piazza dei Cavalieri 7, 56126, Pisa, Italy.
Angew Chem Int Ed Engl. 2023 Nov 6;62(45):e202312521. doi: 10.1002/anie.202312521. Epub 2023 Oct 2.
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 S →S transition, with the strongest signal enhancement of Raman and ROA spectral bands below about 800 cm . 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.
具有高灵敏度的共振拉曼光学活性（RROA）光谱揭示了分子结构、手性和激发电子性质的细节。尽管测量存在困难，但钴（III）与S,S - N,N - 乙二胺二琥珀酸配合物的记录数据质量卓越，再结合理论，出色地记录了共振中的分子行为。这包括手性散射的巨大增强、反对称极化率对信号的贡献以及显著塑造光谱的赫茨伯格 - 泰勒效应。手性成分比类似的铝配合物大约大一个数量级。基于密度泛函和振动理论的模拟证实了谱带归属和强度分布。共振归因于S→S跃迁，拉曼和RROA光谱带在约800 cm以下具有最强的信号增强。对于更高的波数，其他激发电子态以较少共振的方式对散射有贡献。因此，RROA光谱学似乎是研究分析化学、生物学和材料科学中吸收分子的结构和电子态的独特工具。
