Ferrocenes with simple chiral substituents: an in-depth theoretical and experimental VCD and ECD study

Patti, Angela; Pedotti, Sonia; Mazzeo, Giuseppe; Longhi, Giovanna; Abbate, Sergio; Paoloni, Lorenzo; Bloino, Julien; Rampino, Sergio; Barone, Vincenzo

doi:10.1039/c9cp00437h

Cited by 20 publications

(18 citation statements)

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“…Closely related to RROA and VCD in LLES are studies involving chiral plasmonic metallic nanoparticles, graphene, chiral fullerenes and nanotubes, and related metallic or extended pi‐electron systems where extensive electronic motion or electronic‐vibrational coupling is especially important, often leading to enhanced VCD and ROA intensities compared with VOA intensities in normal isolated organic small molecules. Examples of such recent work which should lead to interesting new developments in the future of measured and calculated enhanced VOA are from previous studies …”

Section: Future Development and Challenges For Voamentioning

confidence: 99%

Vibrational optical activity: From discovery and development to future challenges

Nafie

2020

Chirality

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Vibrational optical activity (VOA) consisting of infrared vibrational circular dichroism (VCD) and vibrational Raman optical activity (ROA) was predicted, discovered, and confirmed between 1971 and 1975. My path to VOA was mentored by three pioneers of chirality and vibrational spectroscopy: Professors Albert Moscowitz, Warner L. Peticolas, and Philip J. Stephens, and while they are no longer alive today, the Chirality Medal, my award address, and this paper are dedicated to each of them. Since the discovery of VOA, a number of key advances have made possible the current era of widespread applications. The principal instrumental advances were Fourier-transform VCD (FT-VCD) and multichannel charge coupled detector (CCD) ROA. Computational advances include the first complete quantum chemistry formulation of VCD leading to the magnetic field perturbation (MFP) and the nuclear velocity perturbation (NVP) theories. The strength of VOA is the comparison between measured and calculated spectra that enables the determination of absolute configuration and solution-state conformations. More recently, VCD has uncovered supramolecular chirality in amyloid fibrils and ROA to high-order protein structure. Future challenges for VOA include describing the effects of weak intermolecular interactions, transfer of chirality, solvent effects, supramolecular chirality, and the generation of nuclear velocity electron current density. K E Y W O R D S vibrational circular dichroism (VCD), Raman optical activity (ROA)

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Section: Future Development and Challenges For Voamentioning

confidence: 99%

Vibrational optical activity: From discovery and development to future challenges

Nafie

2020

Chirality

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“…Vibrational motions of molecules can be experimentally probed by several spectroscopic techniques such as infrared, vibrationally resolved electronic and rotational spectroscopies, and significant efforts are devoted in our group to the accurate reproduction of vibrational and vibrationally resolved experimental spectra through computational methods . In the context of conformational analysis of flexible cyclic molecules, a set of useful process coordinates for describing ring‐puckering motions is that devised by Cremer and Pople, the so‐called ring‐puckering coordinates (see also Ref.…”

Section: Pes and Dimensionality Reductionmentioning

confidence: 99%

Chemical promenades: Exploring potential‐energy surfaces with immersive virtual reality

et al. 2020

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The virtual-reality framework AVATAR (Advanced Virtual Approach to Topological Analysis of Reactivity) for the immersive exploration of potential-energy landscapes is presented. AVATAR is based on modern consumer-grade virtual-reality technology and builds on two key concepts: (a) the reduction of the dimensionality of the potential-energy surface to two process-tailored, physically meaningful generalized coordinates, and (b) the analogy between the evolution of a chemical process and a pathway through valleys (potential wells) and mountain passes (saddle points) of the associated potential energy landscape. Examples including the discovery of competitive reaction paths in simple A + BC collisional systems and the interconversion between conformers in ring-puckering motions of flexible rings highlight the innovation potential that augmented and virtual reality convey for teaching, training, and supporting research in chemistry. K E Y W O R D S atom diatom reactions, immersive virtual reality, potential energy surface, ring puckering motions 1 | INTRODUCTION As well known, rigorous simulations of molecular processes should be based on the solution of the Schrödinger equation for the wavefunction of the involved nuclei and electrons, which is usually cast in its nonrelativistic time-independent form with a Hamiltonian including a kinetic term for the electronsT e , a kinetic term for the nucleiT N , and an interaction-potential term V (r, R), with r and R being the set of spatial coordinates of electrons and nuclei, respectively.This equation is seldom solved as is, due to the associated mathematical difficulties and computational cost. More commonly, on the grounds that the nuclei are much heavier than the electrons, the Born-Oppenheimer approximation [1] is adopted and the problem is broken down in two separate problems, one for the motion of the electrons at a given nuclear geometry:T

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“…Ferrocene is an inherently achiral organometallic chromophore which spectral band attributable to d‐d transitions in the iron atom lies in the visible region ( λ ∼450 nm), far from the absorption maxima of common solvents and other organic chromophores. The chiroptical activity of ferrocene is induced by an asymmetric environment, which may arise from the incorporation of stereogenic centers, [7] binding of chiral ligands and interaction with chiral hosts, [8] supramolecular assembly, [9] etc. Activity in the visible range of CD spectra is also characteristic of numerous ferrocene peptidomimetics, compounds that mimic the secondary structure of natural peptides, prepared by incorporating peptide chains into amino‐ and carboxyl‐functionalized ferrocene scaffolds [10–14] .…”

Section: Introductionmentioning

confidence: 99%

Sensing of the Induced Helical Chirality by the Chiroptical Response of the Ferrocene Chromophore

et al. 2021

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The experimental (infrared, nuclear magnetic resonance, circular dichroism) and computational (density functional theory) methods allowed us to demonstrate the potential of the ferrocene chromophore to translate chiral information stored at N‐terminally attached l‐Ala, and transmitted through achiral (Aib)n sequence (n=1 to 3), into a characteristic signal in circular dichroism spectra near 470 nm. The sufficiently long tetrapeptide forms a robust and highly organized 310 helices capable of perturbing the environment of the highly symmetric ferrocene chromophore in an asymmetric manner. The origin of the sign in the circular dichroism spectra of the ferrocene chromophore (near the 470 nm) strongly correlates with the sign of the dihedral angle χ, accounting for a rotation of a substituent attached to the cyclopentadienyl ring that depends on the helicity of peptide sequence. These observations may help us in the design of future ferrocene‐based probes for the assignment of the screw‐sense preference of short peptides.

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Ferrocenes with simple chiral substituents: an in-depth theoretical and experimental VCD and ECD study

Abstract: Ferrocenes bearing chiral pendants are investigated through VCD and ECD. The VCD spectra are best interpreted by GVPT2-anharmonic DFT calculations. Diagnostic bands related to the absolute configuration of the title compounds are found in both kinds of spectra.

Cited by 20 publications

References 59 publications

Vibrational optical activity: From discovery and development to future challenges

Vibrational optical activity: From discovery and development to future challenges

Chemical promenades: Exploring potential‐energy surfaces with immersive virtual reality

Sensing of the Induced Helical Chirality by the Chiroptical Response of the Ferrocene Chromophore

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