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Carbo-Cages: A Computational Study

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Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), and Donostia International Physics Center (DIPC), P. K. 1072, 20080 Donostia, Euskadi, Spain
Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados, Unidad Mérida, Km 6 Antigua Carretera a Progreso. Apdo. Postal 73, Cordemex, 97310, Mérida, Yuc., México
§ Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, Ciudad Universitaria, 72570, Puebla, Pue., México
Department of Chemistry and Centre for Theoretical Studies, Indian Institute of Technology, Kharagpur, 721302, India
Unidad Académica de Ciencias Químicas, Área de Ciencias de la Salud, Universidad Autónoma de Zacatecas, Km. 6 carretera Zacatecas-Guadalajara s/n, Ejido La Escondida C. P. 98160, Zacatecas, Zac., Mexico
*E-mail: [email protected] (G.M.).
*E-mail: [email protected] (J.M.U.).
Cite this: J. Org. Chem. 2014, 79, 12, 5463–5470
Publication Date (Web):May 20, 2014
https://doi.org/10.1021/jo500488c
Copyright © 2014 American Chemical Society

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    Abstract

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    Inspired by their geometrical perfection, intrinsic beauty, and particular properties of polyhedranes, a series of carbo-cages is proposed in silico via density functional theory computations. The insertion of alkynyl units into the C–C bonds of polyhedranes results in a drastic lowering of the structural strain. The induced magnetic field shows a significant delocalization around the three-membered rings. For larger rings, the response is paratropic or close to zero, suggesting a nonaromatic behavior. In the carbo-counterparts, the values of the magnetic response are shifted with respect to their parent compounds, but the aromatic/nonaromatic character remains unaltered. Finally, Born–Oppenheimer molecular dynamics simulations at 900 K do not show any drastic structural changes up to 10 ps. In the particular case of a carbo-prismane, no structural change is perceived until 2400 K. Therefore, although carbo-cages have enthalpies of formation 1 order of magnitude higher than those of their parent compounds, their future preparation and isolation should not be discarded, because the systems are kinetically stable, explaining why the similar systems like carbo-cubane have already been synthesized.

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    The geometries of the parent polyhedranes and enthalpies of formation and geometrical parameters of cubane and carbo-cubane computed using different functionals. Born–Oppenheimer molecular dynamics simulation movies at 900 K for carbo-1 to carbo-9 in mp4 format are provided in a compressed zip file. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 13 publications.

    1. David Arias-Olivares, Andrés Becerra-Buitrago, Luis Carlos García-Sánchez, Diego V. Moreno, Rafael Islas. In Silico Analysis of the Aromaticity of Some Carbo-Metallabenzenes and Carbo-Dimetallabenzenes (Carbo-mers Proposed from Metallabenzenes). ACS Omega 2024, 9 (9) , 10913-10928. https://doi.org/10.1021/acsomega.3c10049
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    3. Filipe Agapito, Rui C. Santos, Rui M. Borges dos Santos, and José A. Martinho Simões . The Thermochemistry of Cubane 50 Years after Its Synthesis: A High-Level Theoretical Study of Cubane and Its Derivatives. The Journal of Physical Chemistry A 2015, 119 (12) , 2998-3007. https://doi.org/10.1021/jp511756v
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    9. Yenni P. Ortiz, Douglas J. Klein, Joel F. Liebman. Paradigms and paradoxes. Tetrahedral units: dodecahedral super-structures. Structural Chemistry 2018, 29 (1) , 89-96. https://doi.org/10.1007/s11224-017-1003-2
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    11. Kévin Cocq, Christine Lepetit, Valérie Maraval, Remi Chauvin. “Carbo-aromaticity” and novel carbo-aromatic compounds. Chemical Society Reviews 2015, 44 (18) , 6535-6559. https://doi.org/10.1039/C5CS00244C
    12. Fabio Pichierri. Hypercubane: DFT-based prediction of an O-symmetric double-shell hydrocarbon. Chemical Physics Letters 2014, 612 , 198-202. https://doi.org/10.1016/j.cplett.2014.08.032
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