Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry

Pyrogallol[4]arenes are macrocycles with high potential as building blocks for nanocapsules. We theoretically studied the dimeric precursors of 2,8,14,20-tetramethylpyrogallol[4]arene and 2,8,10,14-tetraphenylpyrogallol[4] arene to understand the dynamics of assembly of these compounds, and calculat...

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Main Authors: Robert A. Cazar, F. Javier Torres
Format: Article
Language:English
Published: Pontificia Universidad Javeriana 2014-05-01
Series:Universitas Scientiarum
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Online Access:http://revistas.javeriana.edu.co/index.php/scientarium/article/view/8472/7411
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author Robert A. Cazar
F. Javier Torres
author_facet Robert A. Cazar
F. Javier Torres
author_sort Robert A. Cazar
collection DOAJ
description Pyrogallol[4]arenes are macrocycles with high potential as building blocks for nanocapsules. We theoretically studied the dimeric precursors of 2,8,14,20-tetramethylpyrogallol[4]arene and 2,8,10,14-tetraphenylpyrogallol[4] arene to understand the dynamics of assembly of these compounds, and calculated the potential energy curves along the torsion angle of the (R-pyrogallol)CH–(R-pyrogallol) dimeric bond at the B3LYP/6-311G(d,p) level of theory. We found that the energy barriers for free rotation around the selected bond are 0.00133 Hartrees for the alkyl-substituted dimer and 0.77879 Hartrees for the aryl-substituted dimer. These values imply that the free rotation around the selected bond exists for the first dimer but not for the second one. Because the orientation of the substituent and the pyrogallol ring around this bond are likely to determine the geometry of the final structure, we propose that the alkyl-substituted compound will most likely adopt a crown-shaped geometry whereas the aryl-substituted compound will adopt a chair-shaped geometry. These predictions concur with experimental evidence, which shows that the geometry of pyrogallol[4]arenes depends on the substituents attached to them.
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spelling doaj-art-bd87b08b59f744ca98b0f6d0ac7fd5cd2025-08-20T02:00:29ZengPontificia Universidad JaverianaUniversitas Scientiarum0122-74830122-74832014-05-0119113313710.11144/Javeriana.SC19-2.tirbTheoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometryRobert A. Cazar0 F. Javier Torres1 ESPOCH, Facultad de Ciencias, Panamericana Sur Km 1.5, Riobamba, Ecuador Grupo de Química Computacional y Teórica (QCT-USFQ), Universidad San Francisco de Quito, Diego de Robles y Vía Interoceánica, Quito 17-1200-841, Ecuador.Pyrogallol[4]arenes are macrocycles with high potential as building blocks for nanocapsules. We theoretically studied the dimeric precursors of 2,8,14,20-tetramethylpyrogallol[4]arene and 2,8,10,14-tetraphenylpyrogallol[4] arene to understand the dynamics of assembly of these compounds, and calculated the potential energy curves along the torsion angle of the (R-pyrogallol)CH–(R-pyrogallol) dimeric bond at the B3LYP/6-311G(d,p) level of theory. We found that the energy barriers for free rotation around the selected bond are 0.00133 Hartrees for the alkyl-substituted dimer and 0.77879 Hartrees for the aryl-substituted dimer. These values imply that the free rotation around the selected bond exists for the first dimer but not for the second one. Because the orientation of the substituent and the pyrogallol ring around this bond are likely to determine the geometry of the final structure, we propose that the alkyl-substituted compound will most likely adopt a crown-shaped geometry whereas the aryl-substituted compound will adopt a chair-shaped geometry. These predictions concur with experimental evidence, which shows that the geometry of pyrogallol[4]arenes depends on the substituents attached to them.http://revistas.javeriana.edu.co/index.php/scientarium/article/view/8472/7411Pyrogallol[4]arenescomputational chemistrynanocapsules
spellingShingle Robert A. Cazar
F. Javier Torres
Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
Universitas Scientiarum
Pyrogallol[4]arenes
computational chemistry
nanocapsules
title Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
title_full Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
title_fullStr Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
title_full_unstemmed Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
title_short Theoretical indications on the relationship between pyrogallol[4]arenes dynamics of assembling and geometry
title_sort theoretical indications on the relationship between pyrogallol 4 arenes dynamics of assembling and geometry
topic Pyrogallol[4]arenes
computational chemistry
nanocapsules
url http://revistas.javeriana.edu.co/index.php/scientarium/article/view/8472/7411
work_keys_str_mv AT robertacazar theoreticalindicationsontherelationshipbetweenpyrogallol4arenesdynamicsofassemblingandgeometry
AT fjaviertorres theoreticalindicationsontherelationshipbetweenpyrogallol4arenesdynamicsofassemblingandgeometry