Hammett correlations 'beyond the molecule'

Peter R. Ashton; Matthew C T Fyfe; Sarah K. Hickingbottom; J. Fraser Stoddart; Andrew J P White; David J. Williams

doi:10.1039/a802406e

Hammett correlations 'beyond the molecule'

Peter R. Ashton, Matthew C T Fyfe, Sarah K. Hickingbottom, J. Fraser Stoddart^*, Andrew J P White, David J. Williams

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

113 Scopus citations

Abstract

The crown ether dibenzo[24]crown-8 (DB24C8) is interpenetrated by a wide range of disubstituted dibenzylammonium cations to generate [2]pseudorotaxane complexes by virtue of, inter alia, hydrogen bonds. ¹H NMR spectroscopic measurements indicate that the solution phase binding strengths of the pseudorotaxane complexes can be controlled accurately via judicious manipulation of the substituents attached to the dibenzylammonium cations' aryl rings. A linear free energy relationship (LFER) has been found to exist between the complexes' stability constants (K_as) and the Hammett substituent constants (σ). X-Ray crystallographic analyses of the pseudorotaxanes reveal that each of their discrete supramolecular units display similar solid state superstructures. However, these analyses also demonstrate that the pseudorotaxanes associate with one another, via a myriad of intersupramolecular packing motifs, to generate a wide range of novel superarchitectures.

Original language	English (US)
Pages (from-to)	2117-2128
Number of pages	12
Journal	Journal of the Chemical Society. Perkin Transactions 2
Issue number	10
DOIs	https://doi.org/10.1039/a802406e
State	Published - Oct 1998

ASJC Scopus subject areas

General Chemistry

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title = "Hammett correlations 'beyond the molecule'",

abstract = "The crown ether dibenzo[24]crown-8 (DB24C8) is interpenetrated by a wide range of disubstituted dibenzylammonium cations to generate [2]pseudorotaxane complexes by virtue of, inter alia, hydrogen bonds. 1H NMR spectroscopic measurements indicate that the solution phase binding strengths of the pseudorotaxane complexes can be controlled accurately via judicious manipulation of the substituents attached to the dibenzylammonium cations' aryl rings. A linear free energy relationship (LFER) has been found to exist between the complexes' stability constants (Kas) and the Hammett substituent constants (σ). X-Ray crystallographic analyses of the pseudorotaxanes reveal that each of their discrete supramolecular units display similar solid state superstructures. However, these analyses also demonstrate that the pseudorotaxanes associate with one another, via a myriad of intersupramolecular packing motifs, to generate a wide range of novel superarchitectures.",

author = "Ashton, {Peter R.} and Fyfe, {Matthew C T} and Hickingbottom, {Sarah K.} and Stoddart, {J. Fraser} and White, {Andrew J P} and Williams, {David J.}",

year = "1998",

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doi = "10.1039/a802406e",

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journal = "Journal of the Chemical Society. Perkin Transactions 2",

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T1 - Hammett correlations 'beyond the molecule'

AU - Ashton, Peter R.

AU - Fyfe, Matthew C T

AU - Hickingbottom, Sarah K.

AU - Stoddart, J. Fraser

AU - White, Andrew J P

AU - Williams, David J.

PY - 1998/10

Y1 - 1998/10

N2 - The crown ether dibenzo[24]crown-8 (DB24C8) is interpenetrated by a wide range of disubstituted dibenzylammonium cations to generate [2]pseudorotaxane complexes by virtue of, inter alia, hydrogen bonds. 1H NMR spectroscopic measurements indicate that the solution phase binding strengths of the pseudorotaxane complexes can be controlled accurately via judicious manipulation of the substituents attached to the dibenzylammonium cations' aryl rings. A linear free energy relationship (LFER) has been found to exist between the complexes' stability constants (Kas) and the Hammett substituent constants (σ). X-Ray crystallographic analyses of the pseudorotaxanes reveal that each of their discrete supramolecular units display similar solid state superstructures. However, these analyses also demonstrate that the pseudorotaxanes associate with one another, via a myriad of intersupramolecular packing motifs, to generate a wide range of novel superarchitectures.

AB - The crown ether dibenzo[24]crown-8 (DB24C8) is interpenetrated by a wide range of disubstituted dibenzylammonium cations to generate [2]pseudorotaxane complexes by virtue of, inter alia, hydrogen bonds. 1H NMR spectroscopic measurements indicate that the solution phase binding strengths of the pseudorotaxane complexes can be controlled accurately via judicious manipulation of the substituents attached to the dibenzylammonium cations' aryl rings. A linear free energy relationship (LFER) has been found to exist between the complexes' stability constants (Kas) and the Hammett substituent constants (σ). X-Ray crystallographic analyses of the pseudorotaxanes reveal that each of their discrete supramolecular units display similar solid state superstructures. However, these analyses also demonstrate that the pseudorotaxanes associate with one another, via a myriad of intersupramolecular packing motifs, to generate a wide range of novel superarchitectures.

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JF - Journal of the Chemical Society. Perkin Transactions 2

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Hammett correlations 'beyond the molecule'

Abstract

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