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Encapsulated guest-host dynamics: guest rotational barriers and tumbling as a probe of host interior cavity space.

The supramolecular host assembly [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) encapsulates cationic guest molecules within its hydrophobic cavity and catalyzes a variety of chemical transformations within its confined interior space. Despite the well-defined structure, the ho... Full description

Journal Title: Journal of the American Chemical Society November 17, 2010, Vol.132(45), pp.16256-16264
Main Author: Mugridge, Jeffrey S
Other Authors: Szigethy, Géza , Bergman, Robert G , Raymond, Kenneth N
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1520-5126 ; DOI: 1520-5126 ; DOI: 10.1021/ja107656g
Link: http://search.proquest.com/docview/814464464/?pq-origsite=primo
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title: Encapsulated guest-host dynamics: guest rotational barriers and tumbling as a probe of host interior cavity space.
format: Article
creator:
  • Mugridge, Jeffrey S
  • Szigethy, Géza
  • Bergman, Robert G
  • Raymond, Kenneth N
subjects:
  • Capsules–Chemistry
  • Gallium–Chemistry
  • Magnetic Resonance Spectroscopy–Chemistry
  • Organometallic Compounds–Chemistry
  • X-Ray Diffraction–Chemistry
  • Capsules
  • Organometallic Compounds
  • Gallium
ispartof: Journal of the American Chemical Society, November 17, 2010, Vol.132(45), pp.16256-16264
description: The supramolecular host assembly [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) encapsulates cationic guest molecules within its hydrophobic cavity and catalyzes a variety of chemical transformations within its confined interior space. Despite the well-defined structure, the host ligand framework and interior cavity are very flexible and 1 can accommodate a wide range of guest shapes and sizes. These observations raise questions about the steric effects of confinement within 1 and how encapsulation fundamentally changes the motions of guest molecules. Here we examine the motional dynamics (guest bond rotation and tumbling) of encapsulated guest molecules to probe the steric consequences of encapsulation within host 1. Encapsulation is found to increase the Ph-CH(2) bond rotational barrier for ortho-substituted benzyl phosphonium guest molecules by 3 to 6 kcal/mol, and the barrier is found to depend on both guest size and shape. The tumbling dynamics of guests encapsulated in 1 were also investigated, and here it was found that longer, more prolate-shaped guest molecules tumble more slowly in the host cavity than larger but more spherical guest molecules. The prolate guests reduce the host symmetry from T to C(1) in solution at low temperatures, and the distortion of the host framework that is in part responsible for this symmetry reduction is observed directly in the solid state. Analysis of guest motional dynamics is a powerful method for interrogating host structure and fundamental host-guest interactions.
language: eng
source:
identifier: E-ISSN: 1520-5126 ; DOI: 1520-5126 ; DOI: 10.1021/ja107656g
fulltext: no_fulltext
issn:
  • 15205126
  • 1520-5126
url: Link


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titleEncapsulated guest-host dynamics: guest rotational barriers and tumbling as a probe of host interior cavity space.
creatorMugridge, Jeffrey S ; Szigethy, Géza ; Bergman, Robert G ; Raymond, Kenneth N
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descriptionThe supramolecular host assembly [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) encapsulates cationic guest molecules within its hydrophobic cavity and catalyzes a variety of chemical transformations within its confined interior space. Despite the well-defined structure, the host ligand framework and interior cavity are very flexible and 1 can accommodate a wide range of guest shapes and sizes. These observations raise questions about the steric effects of confinement within 1 and how encapsulation fundamentally changes the motions of guest molecules. Here we examine the motional dynamics (guest bond rotation and tumbling) of encapsulated guest molecules to probe the steric consequences of encapsulation within host 1. Encapsulation is found to increase the Ph-CH(2) bond rotational barrier for ortho-substituted benzyl phosphonium guest molecules by 3 to 6 kcal/mol, and the barrier is found to depend on both guest size and shape. The tumbling dynamics of guests encapsulated in 1 were also investigated, and here it was found that longer, more prolate-shaped guest molecules tumble more slowly in the host cavity than larger but more spherical guest molecules. The prolate guests reduce the host symmetry from T to C(1) in solution at low temperatures, and the distortion of the host framework that is in part responsible for this symmetry reduction is observed directly in the solid state. Analysis of guest motional dynamics is a powerful method for interrogating host structure and fundamental host-guest interactions.
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