Unexpected influence of substituents on the binding affinities of polycyclic aromatic hydrocarbons with a tetra-Au(I) metallorectangle
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Título
Unexpected influence of substituents on the binding affinities of polycyclic aromatic hydrocarbons with a tetra-Au(I) metallorectangleFecha de publicación
2020-11-02ISSN
0276-7333; 1520-6041Cita bibliográfica
Ibáñez, S., Gusev, D., & Peris, E. (2020). Unexpected Influence of Substituents on the Binding Affinities of Polycyclic Aromatic Hydrocarbons with a Tetra-Au(I) Metallorectangle. Organometallics, 39(22), 4078-4084. doi: 10.1021/acs.organomet.0c00639Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
https://pubs.acs.org/doi/10.1021/acs.organomet.0c00639Versión
info:eu-repo/semantics/acceptedVersionPalabras clave / Materias
Resumen
A tetra-gold supramolecular organometallic cage constructed with two pyrene-bis-imidazolylidene ligands
and two carbazolyl-bis-alkynyl linkers (1) was studied as host for a series of substituted polycyclic aromatic ... [+]
A tetra-gold supramolecular organometallic cage constructed with two pyrene-bis-imidazolylidene ligands
and two carbazolyl-bis-alkynyl linkers (1) was studied as host for a series of substituted polycyclic aromatic
hydrocarbons (PAHs). For the two smaller PAHs used (2-naphthalenol and 1-pyrenemethanol), the presence of the -
OH groups at the periphery of the molecules did not enhance the binding affinity of the guest, compared with the
unsubstituted PAHs. This observation indicated no hydrogen bonding of these two guests with the NH of the carbazole
linker, as well as negligible dispersive interactions of the substituents with the π-system of 1. In the case of 3-
perylenemethanol, the CH2OH group produced a significant increase in the binding affinity, vs perylene. Similarly, 3-
methylperylene shows an increased binding affinity compared to perylene. MN15-L/def2-QZVP calculations gave Gibbs
reaction energies for the displacement of perylene from the host by the substituted perylenes becoming more exergonic
in the order: -1.6 (3-methylperylene) > -4.3 (3-ethylperylene) > -4.5 kcal/mol (3-perylenemethanol). The experimental
and DFT results indicate that the peripheral dispersive interactions can make a significant contribution to the host-guest
bonding energy, in addition to the conventional π–π stacking interactions. Our work highlights the importance of
dispersive interactions in the contribution to the binding affinity of host-guest chemistry complexes [-]
Publicado en
Organometallics Volume 39, Issue 22 (November 23, 2020)Entidad financiadora
Ministerio de Ciencia y Universidades | Universitat Jaume I
Código del proyecto o subvención
PGC2018- 093382-B-I00 | UJI-B2017- 07 | UJI-A2017-02
Derechos de acceso
http://rightsstatements.org/vocab/CNE/1.0/
info:eu-repo/semantics/openAccess
info:eu-repo/semantics/openAccess
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