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Chirality-Helicity of Cumulenes: A Non-Scalar Charge Density Derived Perspective
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  • Hui Xing,
  • Alireza Azizi,
  • Roya Momen,
  • Tianlv Xu,
  • Steven Kirk,
  • Samantha Jenkins
Hui Xing
Hunan Normal University
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Alireza Azizi
Henan Normal University
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Roya Momen
Central South University
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Tianlv Xu
Hunan Normal University
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Steven Kirk
Hunan Normal University
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Samantha Jenkins
Hunan Normal University
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Abstract

We investigate the presence of helical character and chirality using a vector-based charge density perspective instead of energetic or structural measures. The vector-based perspective of the chemical bonding, constructed using the most preferred direction of charge density accumulation, finds the presence of induced symmetry-breaking for α,ω-disubstituted [4]cumulenes as the end groups are torsioned. The stress tensor trajectories Tσ(s) are used to provide the additional symmetry-breaking required to quantify the degree and nature of the chirality and helical character. We find an absence of chirality for [4]cumulene but a very significant degree of axiality as demonstrated by the purely axial form of the Tσ(s) indicating a lack of helical character. The S-1,5-dimethyl-[4]cumulene contains a very low degree of chiral character but significant axiality(helicity) resulting in a weakly helical morphology of the corresponding Tσ(s). The (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene contain very significant degrees of both chirality and helical character resulting in helical morphology of the corresponding Tσ(s). The chirality assignments are in agreement with the Cahn–Ingold–Prelog (CIP) classifications for the (-)S(-), (+)S(-) and (+)S(+) conformations of S-1,5-diamino-[4]cumulene. We discuss the consequences for the Tσ(s) in locating chiral character in these molecules in future experiment investigations.
06 Nov 2021Submitted to International Journal of Quantum Chemistry
06 Nov 2021Submission Checks Completed
06 Nov 2021Assigned to Editor
09 Nov 2021Reviewer(s) Assigned
08 Dec 2021Review(s) Completed, Editorial Evaluation Pending
17 Dec 2021Editorial Decision: Revise Major
21 Dec 20211st Revision Received
21 Dec 2021Submission Checks Completed
21 Dec 2021Assigned to Editor
21 Dec 2021Reviewer(s) Assigned
05 Jan 2022Review(s) Completed, Editorial Evaluation Pending
05 Jan 2022Editorial Decision: Accept
15 May 2022Published in International Journal of Quantum Chemistry volume 122 issue 10. 10.1002/qua.26884