Recognition of the True and False Resonance Raman Optical Activity

Barańska, Małgorzata; Machalska, Ewa; Zając, Grzegorz; Wierzba, Aleksandra J.; Kapitán, Josef; Andruniów, Tadeusz; Spiegel, Maciej; Gryko, Dorota; Bouř, Petr

doi:10.1002/anie.202107600

Cited by 28 publications

(57 citation statements)

References 46 publications

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“…The factor ln10 is added since decadic absorption coefficients are used. [24,25] A step-by-step derivation of equation ( 1) was provided in Ref. [23] and a brief summary is given below.…”

Section: The Discovery Of Ecp-raman Spectroscopymentioning

confidence: 99%

“…A slight modification of equation ( 1) was proposed to account for the difference in the ECD versus Raman/ROA active path. [25] With this tool in hand, it is now possible to simulate eCP-Raman spectra of solvents which are not under resonance themselves.…”

Section: The Discovery Of Ecp-raman Spectroscopymentioning

confidence: 99%

“…The possibility to extract RROA features was discussed by Machalska et al [25] working with a series of Vitamin B 12 derivates. In the I R À I L measurements of some Vitamin B 12 derivatives, the authors observed a pronounced dependence of the I R À I L signs on the concentration of B 12 .…”

Section: Conflict Of Interestmentioning

confidence: 99%

“…A few different phases have been used to describe this new form of chiral Raman spectroscopy, for example, ‘two spectroscopies in one: interference of CD and ROA’, [23] eCP‐Raman , a combination of electronic circular dichroism and circularly polarized Raman, [24] false ROA and ECD/ROA interference, [25] and ECD‐Raman [26] . We will adopt the usage of a combination of ECD and circularly polarized‐Raman (CP‐Raman) [7] and abbreviate it as e CP‐Raman to emphasize the contribution of both ECD and CP‐Raman in this mechanism.…”

Section: Introductionmentioning

confidence: 99%

“…c is the concentration of the chiral solute, L is the optical path length, DOC is the normalized degree of circularity of the vibrational transition of interest, and I R and I L are the intensities of scattered RCPL and LCPL registered at the ROA instrument, respectively. The factor ln10 is added since decadic absorption coefficients are used [24,25] . A step‐by‐step derivation of equation (1) was provided in Ref.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Circular Dichroism‐Circularly Polarized Raman (eCP‐Raman): A New Form of Chiral Raman Spectroscopy

Al-Shalalfeh

Kapitán

et al. 2022

Chemistry A European J

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This Concept article summarizes recent work on the development of a new form of chiral Raman spectroscopy, eCP-Raman, which combines two spectroscopies: electronic circular dichroism (ECD) and circularly polarized Raman (CP-Raman). First, some puzzling observations while carrying out Raman optical activity (ROA) measurements of several transition metal complexes under resonance are described, as well as the search for the mechanisms responsible. Then an equation for quantifying the eCP-Raman contribution is presented, followed by several examples of how eCP-Raman influences the I R À I L spectra of achiral and chiral solvent molecules and of a number of chiral solutes under resonance. The conditions to extract resonance ROA, when the eCP-Raman contribution is minimized, are also discussed. Finally, we comment on the potential applications of eCP-Raman.

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“…The factor ln10 is added since decadic absorption coefficients are used. [24,25] A step-by-step derivation of equation ( 1) was provided in Ref. [23] and a brief summary is given below.…”

Section: The Discovery Of Ecp-raman Spectroscopymentioning

confidence: 99%

Section: The Discovery Of Ecp-raman Spectroscopymentioning

confidence: 99%

Section: Conflict Of Interestmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Electronic Circular Dichroism‐Circularly Polarized Raman (eCP‐Raman): A New Form of Chiral Raman Spectroscopy

Al-Shalalfeh

Kapitán

et al. 2022

Chemistry A European J

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Chiral Nanostructured Bimetallic Au–Ag Films for Enantiomeric Discrimination

Deng

Duan

et al. 2022

Adv Materials Inter

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circular dichroism, [3] electronic circular dichroism [4] and Raman optical activity, [5] has been used in both quantitative analysis and absolute configuration study of the enantiomers. However, the feasibility of enantiomeric discrimination by chiral chromatography strongly depends on molecular polarity and mass of enantiomers, which narrows applicable conditions and molecules for each chiral column. Chiral spectroscopy is impossible to be used for enantioselective discrimination of racemates or chiral molecules with inherently weak optical response suffering from poor resolution and low sensitivity. [6] Recently, we developed new strategies, PM-ChA [7] and SERS-ChA [8] of chiral nanostructured Au films (CNAFs) to enantiomers, which demonstrated enantiomeric determination, based on the selective generation of photomagnetic fields (PMFs) and selective enhancement of Raman scattering of enantiomeric molecules on CNAFs, respectively. These methods are available for all the enantiomers regardless of their sizes, polarities, or chromophores, which overcome the drawbacks of chromatography and spectroscopy.Silver (Ag) nanomaterials show strong SPR effects and excellent electrical conductivity, making them promising for plasmonic sensing systems and optoelectronic devices. [9] Therefore, doping with Ag should allow modulating the SPR and increasing conductivity of composite nanomaterials, which is expected to generate stronger local electromagnetic fields and further enhance the SERS intensities. This strategy provides the possibility for simultaneous enhancement of the PM-ChA and SERS-ChA effects of chiral noble metal nanomaterials. However, multi-metal compounding by the wet chemical deposition method sometimes suffers from difficulty in finding a reductant with appropriate reducing potential for simultaneous codeposition of metal ions in the precursor solution.Electrodeposition is a universal, efficient, and low-consumption technique for the preparation of Ag containing composite nanomaterials comparing with the other methods, [10] because deposition occurs in a very limited range on the electrode surface and the electrodeposition method allows precisely controlled reduction potential and duration time for Ag material preparation. [11] In addition, reduction reaction rates of different metal ions can be adjusted by changing the reduction potential, which makes them uniformly deposited Herein, the chiral nanostructured bimetallic Au-Ag films (CNAAFs) with both photomagnetic-chiral anisotropy to enantiomers (PM-ChA C-E ) and surface-enhanced Raman scattering-chiral anisotropy to enantiomers (SERS-ChA C-E ) for efficient enantiomeric discrimination are reported. The CNAAFs are synthesized by electrodeposition on n-type Si (n-Si) substrates with the assistance of N-acetyl-L/D-cysteine (S/R-NAC) as symmetry-breaking agents, which are consisted of polycrystalline Boerdijk-Coxeter-Bernal (BCB) tetrahelical structured Au-Ag alloy nanowires grown on n-Si substrates perpendicularly. The anisotropic factors of PM-ChA C-E ...

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

Yang,

Bloino,

Šestáková

et al. 2023

Angewandte Chemie

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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.

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Recognition of the True and False Resonance Raman Optical Activity

Cited by 28 publications

References 46 publications

Electronic Circular Dichroism‐Circularly Polarized Raman (eCP‐Raman): A New Form of Chiral Raman Spectroscopy

Electronic Circular Dichroism‐Circularly Polarized Raman (eCP‐Raman): A New Form of Chiral Raman Spectroscopy

Chiral Nanostructured Bimetallic Au–Ag Films for Enantiomeric Discrimination

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

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