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Title: Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The geometries and binding energies of a recent buckyball tweezers (C60H28) and its supramolecular complexes are investigated using recently developed density functionals (M06-L and M06-2X) that include an accurate treatment of medium-range correlation energy. The pincer part of the tweezers, corannulene, has a strong attractive interaction with C60. However, due to the entropy penalty, the calculated gas-phase free energy of association of the C60@corannulene supramolecule is positive 3.5 kcal mol-1; and this entropy penalty explains why it is difficult to observe C60@corannulene supramolecule experimentally. By using a p-extended tetrathiafulvalene (TTF), in particular 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (TTFAQ or C20H10S4), as the pincer part, we modeled a new buckyball tweezers. The geometries and binding energies of the new buckyball tweezers and its supramolecular complexes are also calculated. Due to fact that the attractive interaction between TTFAQ and C60 is weaker than that between corannulene and C60, the gas-phase binding free energy in the C60@C60H 32S8 supramolecular complex is smaller than that in the C60@C60H28more » supramolecule. We also discuss solvent effects.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
959204
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP, 10:2813-2818
Additional Journal Information:
Journal Volume: 10; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRON CORRELATION; ENTROPY; FREE ENERGY; DENSITY FUNCTIONAL METHOD; SOLVENTS; TETRATHIAFULVALENE; FULLERENES; MATHEMATICAL MODELS; BINDING ENERGY; Environmental Molecular Sciences Laboratory

Citation Formats

Zhao, Yan, and Truhlar, Donald G. Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions. United States: N. p., 2008. Web. doi:10.1039/b717744e.
Zhao, Yan, & Truhlar, Donald G. Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions. United States. https://doi.org/10.1039/b717744e
Zhao, Yan, and Truhlar, Donald G. Mon . "Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions". United States. https://doi.org/10.1039/b717744e.
@article{osti_959204,
title = {Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions},
author = {Zhao, Yan and Truhlar, Donald G},
abstractNote = {The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The geometries and binding energies of a recent buckyball tweezers (C60H28) and its supramolecular complexes are investigated using recently developed density functionals (M06-L and M06-2X) that include an accurate treatment of medium-range correlation energy. The pincer part of the tweezers, corannulene, has a strong attractive interaction with C60. However, due to the entropy penalty, the calculated gas-phase free energy of association of the C60@corannulene supramolecule is positive 3.5 kcal mol-1; and this entropy penalty explains why it is difficult to observe C60@corannulene supramolecule experimentally. By using a p-extended tetrathiafulvalene (TTF), in particular 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene (TTFAQ or C20H10S4), as the pincer part, we modeled a new buckyball tweezers. The geometries and binding energies of the new buckyball tweezers and its supramolecular complexes are also calculated. Due to fact that the attractive interaction between TTFAQ and C60 is weaker than that between corannulene and C60, the gas-phase binding free energy in the C60@C60H 32S8 supramolecular complex is smaller than that in the C60@C60H28 supramolecule. We also discuss solvent effects.},
doi = {10.1039/b717744e},
url = {https://www.osti.gov/biblio/959204}, journal = {Physical Chemistry Chemical Physics. PCCP, 10:2813-2818},
issn = {1463-9076},
number = ,
volume = 10,
place = {United States},
year = {2008},
month = {2}
}