Herringbone Pattern and CH–π Bonding in the Crystal Architecture of Linear Polycyclic Aromatic Hydrocarbons
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Título: | Herringbone Pattern and CH–π Bonding in the Crystal Architecture of Linear Polycyclic Aromatic Hydrocarbons |
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Autor/es: | Guijarro, Albert | Vergés Brotons, José Antonio | San-Fabián, Emilio | Chiappe, Guillermo | Louis, Enrique |
Grupo/s de investigación o GITE: | Nuevos Materiales y Catalizadores (MATCAT) | Química Cuántica | Física de la Materia Condensada | Materiales Avanzados |
Centro, Departamento o Servicio: | Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Departamento de Física Aplicada | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica |
Palabras clave: | Aromatic hydrocarbons | CH–p bonding | Herringbone pattern | Molecular crystals | Sublimation enthalpies |
Área/s de conocimiento: | Química Orgánica | Química Física | Física Aplicada | Física de la Materia Condensada |
Fecha de publicación: | 4-nov-2016 |
Editor: | Wiley-VCH Verlag GmbH & Co. KGaA |
Cita bibliográfica: | ChemPhysChem. 2016, 17(21): 3548-3557. doi:10.1002/cphc.201600586 |
Resumen: | The herringbone pattern is a pervasive structural motive found in most molecular crystals involving aromatic compounds. A plot of the experimental sublimation enthalpies of members of increasing size of the acene, phenacene and p-phenyl families versus the number of carbons uncovers a linear relationship between the two magnitudes, suggesting a major role of CH–π bonding. In this work we undertake the task of evaluating the relevance of the edge-to-face interaction (or CH–π bond) in the overall reticular energy of the crystal, to quantitatively assess the importance of this structural element. Following a heuristic approach, we considered the series of acenes, phenacenes and p-phenyls and analyzed the edge-to-face interaction between the molecules as they occur in the experimental crystal network. Isolation of the relevant molecular dimers allows to incorporate some of the most sophisticated tools of quantum chemistry and get a reliable picture of the isolated bond. When compared to the experimental sublimation energy, our results are conclusive: this sole interaction is the largest contribution to the lattice energy, and definitively dictates the crystal architecture in all the studied cases. Elusive enough, the edge-to-face interaction is mainly dominated by correlation interactions, specifically in the form of dispersion and, to a less extent, of charge-transfer terms. A suggestive picture of the bond has been obtained by displaying the differences in local electron densities calculated by either correlated or non-correlated methods. |
Patrocinador/es: | Financial support by the spanish “Ministerio de Ciencia e Innovación MICINN” (grants CTQ2011-24165, FIS2012-33521 and FIS2012-35880) and the Universidad de Alicante is gratefully acknowledged. We also acknowledge support from the DGUI of the Comunidad de Madrid under the R&D Program of activities MODELICO-CM/S2009ESP-1691. |
URI: | http://hdl.handle.net/10045/65015 |
ISSN: | 1439-4235 (Print) | 1439-7641 (Online) |
DOI: | 10.1002/cphc.201600586 |
Idioma: | eng |
Tipo: | info:eu-repo/semantics/article |
Derechos: | © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim |
Revisión científica: | si |
Versión del editor: | http://dx.doi.org/10.1002/cphc.201600586 |
Aparece en las colecciones: | INV - MATCAT - Artículos de Revistas INV - QC - Artículos de Revistas INV - Física de la Materia Condensada - Artículos de Revistas INV - LMA - Artículos de Revistas |
Archivos en este ítem:
Archivo | Descripción | Tamaño | Formato | |
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2016_Guijarro_etal_ChemPhysChem_final.pdf | Versión final (acceso restringido) | 1,2 MB | Adobe PDF | Abrir Solicitar una copia |
2016_Guijarro_etal_ChemPhysChem_preprint.pdf | Preprint (acceso abierto) | 1,75 MB | Adobe PDF | Abrir Vista previa |
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