The solid state VCD of a novel N-acylhydrazone trifluoroacetate

Rode, Joanna E.; Łyczko, Krzysztof; Kosińska, Katarzyna; Matalińska, Joanna; Dyniewicz, Jolanta; Misicka, Aleksandra; Dobrowolski, Jan Cz.; Lipiński, Piotr F. J.

doi:10.1016/j.saa.2021.120761

Cited by 9 publications

(5 citation statements)

References 74 publications

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“…In recent years, vibrational circular dichroism (VCD) has come into focus, which is a ground‐state property relying on a wealth of absorption bands (in the infrared region), many more than its electronic counterpart. [11] Being a very sensitive probe of molecular conformation and environment, VCD has been applied to a wide range of molecules including natural products, host‐guest systems, peptides and proteins, nanoparticles or catalysts,[ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 ] supramolecular organisation in the condensed phase,[ 8 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 ] and the formation of chiral phases from achiral subunits. [ 5 , 33 , 34 ] In particular, the utility of solid‐state VCD for the resolution of molecular chirality and supramolecular chirality has been noted by Sato and co‐workers.…”

Section: Introductionmentioning

confidence: 99%

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

et al. 2022

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Solid‐State Vibrational Circular Dichroism (VCD) can be used to determine the absolute structure of chiral crystals, but its interpretation remains a challenge in modern spectroscopy. In this work, we investigate the effect of a twofold screw axis on the solid‐state VCD spectrum in a combined experimental and theoretical analysis of P21 crystals of (S)‐(+)‐1‐indanol. Even though the space group is achiral, a single proper symmetry operation has an important impact on the VCD spectrum, which reflects the supramolecular chirality of the crystal. Distinguishing between contributions originating from molecular chirality and from chiral crystal packing, we find that while IR absorption hardly depends on the symmetry of the space group, the situation is different for VCD, where completely new non‐local patterns emerge. Understanding the two underlying mechanisms, namely gauge transport and direct coupling, will help to use VCD to distinguish polymorphic forms.

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Section: Introductionmentioning

confidence: 99%

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

et al. 2022

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“…[19,86] Nevertheless, there are a number of successful theoretical studies based on molecular clusters being reported. [19,[87][88][89][90][91][92][93][94][95][96][97][98][99][100] Especially for the simpler achiral space groups this approach seems feasible. P2 1 , for instance, contains only two molecules per unit cell, which is straightforwardly translated into a cluster by adding a few more molecules to mitigate the boundary effects.…”

Section: Methodsmentioning

confidence: 99%

“…It is also the finite size effects, the distortion of cluster geometry upon structure optimisation and the introduction of unsaturated non‐covalent interactions that result in biased absorption frequencies and wrong VCD signs [19, 86] . Nevertheless, there are a number of successful theoretical studies based on molecular clusters being reported [19, 87–100] . Especially for the simpler achiral space groups this approach seems feasible.…”

Section: Vibrational Circular Dichroism (Vcd) Theorymentioning

confidence: 99%

Vibrational Circular Dichroism Spectroscopy of Chiral Molecular Crystals: Insights from Theory

Jähnigen

2023

Angew Chem Int Ed

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Chirality is a curious phenomenon that appears in various forms. While the concept of molecular (RS‐)chirality is ubiquitous in chemistry, there are also more intricate forms of structural chirality. One of them is the enantiomorphism of crystals, especially molecular crystals, that describes the lack of mirror symmetry in the unit cell. Its relation to molecular chirality is not obvious, but still an open question, which can be addressed with chiroptical tools. Vibrational circular dichroism (VCD) denotes chiral infrared (IR) spectroscopy that is susceptible to both, the molecular as well as the intermolecular space by means of vibrational transitions. When carried out in the solid state, VCD delivers a very rich set of non‐local contributions that are determined by crystal packing and collective motion. Since its discovery in the 1970s, VCD has become the method of choice for the determination of absolute configurations, but its applicability reaches beyond towards the study of different crystal forms and polymorphism. This brief review summarises the theoretical concepts of crystal chirality and how computations of solid‐state VCD can shed light into the intimate connection of chiral structure and vibrational optical activity.

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“…In recent years, vibrational circular dichroism (VCD) has come into focus, which is a ground-state property relying on a wealth of absorption bands (in the infrared region), many more than its electronic counterpart. [11] Being a very sensitive probe of molecular conformation and environment, VCD has been applied to a wide range of molecules including natural products, host-guest systems, peptides and proteins, nanoparticles or catalysts, [12][13][14][15][16][17][18][19][20][21] supramolecular organisation in the condensed phase, [8,[22][23][24][25][26][27][28][29][30][31][32] and the formation of chiral phases from achiral subunits. [5,33,34] In particular, the utility of solidstate VCD for the resolution of molecular chirality and supramolecular chirality has been noted by Sato and coworkers.…”

Section: Introductionmentioning

confidence: 99%

“…[43,44] In addition, the necessary reference calculations have to suitably account for the supramolecular arrangement of molecules in the crystal. Conventional static DFT calculations applied to isolated molecules or molecular clusters have been successfully used to approximate the system through sub-units extracted from the crystal structure, [5,25,31,32,34,[45][46][47] but this has limited applicability: Boundary effects stemming from the finite size model can substantially alter the frequencies or add artefacts to the spectrum. [24] The result otherwise depends on how well a small cluster describes the crystal.…”

Section: Introductionmentioning

confidence: 99%

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

et al. 2022

View full text Add to dashboard Cite

Solid-State Vibrational Circular Dichroism (VCD) can be used to determine the absolute structure of chiral crystals, but its interpretation remains a challenge in modern spectroscopy. In this work, we investigate the effect of a twofold screw axis on the solid-state VCD spectrum in a combined experimental and theoretical analysis of P2 1 crystals of (S)-(+)-1-indanol. Even though the space group is achiral, a single proper symmetry operation has an important impact on the VCD spectrum, which reflects the supramolecular chirality of the crystal. Distinguishing between contributions originating from molecular chirality and from chiral crystal packing, we find that while IR absorption hardly depends on the symmetry of the space group, the situation is different for VCD, where completely new non-local patterns emerge. Understanding the two underlying mechanisms, namely gauge transport and direct coupling, will help to use VCD to distinguish polymorphic forms.

show abstract

The solid state VCD of a novel N-acylhydrazone trifluoroacetate

Cited by 9 publications

References 74 publications

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

Vibrational Circular Dichroism Spectroscopy of Chiral Molecular Crystals: Insights from Theory

How Crystal Symmetry Dictates Non‐Local Vibrational Circular Dichroism in the Solid State

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