Origins of Selectivity in Molecular and Supramolecular Entities: Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes

Francisco Raymo, K. N. Houk, J. Fraser Stoddart

Research output: Contribution to journalArticle

60 Citations (Scopus)

Abstract

The fundamental basis for the stabilization of molecular complexes of various dioxyarenes and/or dithiaarenes and a tetracationic cyclophane was established by empirical force field and ab initio quantum mechanical calculations. The more stable translational isomers of the related [2]catenanes do not necessarily correspond to the more stable complexes involving the individual components. The origin of this anomaly was investigated using the AMBER* force field. Each [2]catenane is composed of cyclobis(paraquat-p-phenylene)-the tetracationic cyclophane-and one constitutionally unsymmetrical macrocyclic polyether, incorporating 1,4-dioxybenzene and a dioxyarene or a dithiaarene unit as its two π-electron rich recognition sites. The calculated and experimental isomer ratios at equilibrium for these [2]catenanes are in good agreement. In two instances, the calculated ratios invert as a result of changing the solvation model from H2 to CHCl3. There is a correlation between the experimental and theoretical observations for the equilibrated isomer ratios and the dielectric constant of the solvent. Both the solvation energies of the translational isomers and the energy differences associated with the corresponding complexes govern the nature of the translational isomerism. The relative stabilities of isomers are controlled by the electrostatic potential at the surface of the π-electron rich aromatic units, rather than by charge- transfer interactions.

Original languageEnglish
Pages (from-to)6523-6528
Number of pages6
JournalJournal of Organic Chemistry
Volume63
Issue number19
StatePublished - Sep 18 1998
Externally publishedYes

Fingerprint

Catenanes
Isomers
Electrostatics
Solvation
Paraquat
Electrons
Polyethers
Charge transfer
Permittivity
Stabilization

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Origins of Selectivity in Molecular and Supramolecular Entities : Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes. / Raymo, Francisco; Houk, K. N.; Fraser Stoddart, J.

In: Journal of Organic Chemistry, Vol. 63, No. 19, 18.09.1998, p. 6523-6528.

Research output: Contribution to journalArticle

@article{8a409457d5374b60be9900cf5e6315a3,
title = "Origins of Selectivity in Molecular and Supramolecular Entities: Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes",
abstract = "The fundamental basis for the stabilization of molecular complexes of various dioxyarenes and/or dithiaarenes and a tetracationic cyclophane was established by empirical force field and ab initio quantum mechanical calculations. The more stable translational isomers of the related [2]catenanes do not necessarily correspond to the more stable complexes involving the individual components. The origin of this anomaly was investigated using the AMBER* force field. Each [2]catenane is composed of cyclobis(paraquat-p-phenylene)-the tetracationic cyclophane-and one constitutionally unsymmetrical macrocyclic polyether, incorporating 1,4-dioxybenzene and a dioxyarene or a dithiaarene unit as its two π-electron rich recognition sites. The calculated and experimental isomer ratios at equilibrium for these [2]catenanes are in good agreement. In two instances, the calculated ratios invert as a result of changing the solvation model from H2 to CHCl3. There is a correlation between the experimental and theoretical observations for the equilibrated isomer ratios and the dielectric constant of the solvent. Both the solvation energies of the translational isomers and the energy differences associated with the corresponding complexes govern the nature of the translational isomerism. The relative stabilities of isomers are controlled by the electrostatic potential at the surface of the π-electron rich aromatic units, rather than by charge- transfer interactions.",
author = "Francisco Raymo and Houk, {K. N.} and {Fraser Stoddart}, J.",
year = "1998",
month = "9",
day = "18",
language = "English",
volume = "63",
pages = "6523--6528",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "19",

}

TY - JOUR

T1 - Origins of Selectivity in Molecular and Supramolecular Entities

T2 - Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes

AU - Raymo, Francisco

AU - Houk, K. N.

AU - Fraser Stoddart, J.

PY - 1998/9/18

Y1 - 1998/9/18

N2 - The fundamental basis for the stabilization of molecular complexes of various dioxyarenes and/or dithiaarenes and a tetracationic cyclophane was established by empirical force field and ab initio quantum mechanical calculations. The more stable translational isomers of the related [2]catenanes do not necessarily correspond to the more stable complexes involving the individual components. The origin of this anomaly was investigated using the AMBER* force field. Each [2]catenane is composed of cyclobis(paraquat-p-phenylene)-the tetracationic cyclophane-and one constitutionally unsymmetrical macrocyclic polyether, incorporating 1,4-dioxybenzene and a dioxyarene or a dithiaarene unit as its two π-electron rich recognition sites. The calculated and experimental isomer ratios at equilibrium for these [2]catenanes are in good agreement. In two instances, the calculated ratios invert as a result of changing the solvation model from H2 to CHCl3. There is a correlation between the experimental and theoretical observations for the equilibrated isomer ratios and the dielectric constant of the solvent. Both the solvation energies of the translational isomers and the energy differences associated with the corresponding complexes govern the nature of the translational isomerism. The relative stabilities of isomers are controlled by the electrostatic potential at the surface of the π-electron rich aromatic units, rather than by charge- transfer interactions.

AB - The fundamental basis for the stabilization of molecular complexes of various dioxyarenes and/or dithiaarenes and a tetracationic cyclophane was established by empirical force field and ab initio quantum mechanical calculations. The more stable translational isomers of the related [2]catenanes do not necessarily correspond to the more stable complexes involving the individual components. The origin of this anomaly was investigated using the AMBER* force field. Each [2]catenane is composed of cyclobis(paraquat-p-phenylene)-the tetracationic cyclophane-and one constitutionally unsymmetrical macrocyclic polyether, incorporating 1,4-dioxybenzene and a dioxyarene or a dithiaarene unit as its two π-electron rich recognition sites. The calculated and experimental isomer ratios at equilibrium for these [2]catenanes are in good agreement. In two instances, the calculated ratios invert as a result of changing the solvation model from H2 to CHCl3. There is a correlation between the experimental and theoretical observations for the equilibrated isomer ratios and the dielectric constant of the solvent. Both the solvation energies of the translational isomers and the energy differences associated with the corresponding complexes govern the nature of the translational isomerism. The relative stabilities of isomers are controlled by the electrostatic potential at the surface of the π-electron rich aromatic units, rather than by charge- transfer interactions.

UR - http://www.scopus.com/inward/record.url?scp=0000110161&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000110161&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000110161

VL - 63

SP - 6523

EP - 6528

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 19

ER -