Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen

Studies of two newly synthesised, isomeric metal ion-activated molecular receptors, [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(1′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO4)2•H2O and [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(2′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO...

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Main Authors: Smith, C., Buntine, Mark, Lincoln, S., Wainwright, K.
Format: Journal Article
Published: The Royal Society of Chemistry 2003
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/26619
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author Smith, C.
Buntine, Mark
Lincoln, S.
Wainwright, K.
author_facet Smith, C.
Buntine, Mark
Lincoln, S.
Wainwright, K.
author_sort Smith, C.
building Curtin Institutional Repository
collection Online Access
description Studies of two newly synthesised, isomeric metal ion-activated molecular receptors, [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(1′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO4)2•H2O and [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(2′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO4)2, show that both act as molecular receptors for the p-toluenesulfonate anion. The binding cavity depths for the two receptors were calculated from ab initio molecular modelling to be 4.81 and 7.27 Å, respectively. Despite the smaller cavity depth for the first receptor, it forms the more stable inclusion complexes, as assessed by the relative magnitude of the decrease in electrical conductivity and 13C NMR spectral changes. This indicates that hydrogen bonds, from the hydroxyl hydrogen-bond donors at the base of the receptor cavity, rather than π interactions between the aromatic walls of the cavity and the included p-toluenesulfonate are principally responsible for its retention. Nonetheless, the hydrophobic character of the aromatic-binding cavity walls may play a major kinetic role in the formation of the inclusion complexes.
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spelling curtin-20.500.11937-266192017-09-13T15:28:26Z Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen Smith, C. Buntine, Mark Lincoln, S. Wainwright, K. Exponent basis-sets Potentiometric titration Nuclear-magnetic-resonance Compact effective potentials Atoms Efficient Inclusion chemistry Ethers Studies of two newly synthesised, isomeric metal ion-activated molecular receptors, [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(1′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO4)2•H2O and [Cd(1,4,7,10-tetrakis{(S)-(−)-2-hydroxy-3-(2′-naphthyloxy)propyl}-1,4,7,10-tetraazacyclododecane)](ClO4)2, show that both act as molecular receptors for the p-toluenesulfonate anion. The binding cavity depths for the two receptors were calculated from ab initio molecular modelling to be 4.81 and 7.27 Å, respectively. Despite the smaller cavity depth for the first receptor, it forms the more stable inclusion complexes, as assessed by the relative magnitude of the decrease in electrical conductivity and 13C NMR spectral changes. This indicates that hydrogen bonds, from the hydroxyl hydrogen-bond donors at the base of the receptor cavity, rather than π interactions between the aromatic walls of the cavity and the included p-toluenesulfonate are principally responsible for its retention. Nonetheless, the hydrophobic character of the aromatic-binding cavity walls may play a major kinetic role in the formation of the inclusion complexes. 2003 Journal Article http://hdl.handle.net/20.500.11937/26619 10.1039/b305461f The Royal Society of Chemistry restricted
spellingShingle Exponent basis-sets
Potentiometric titration
Nuclear-magnetic-resonance
Compact effective potentials
Atoms
Efficient
Inclusion chemistry
Ethers
Smith, C.
Buntine, Mark
Lincoln, S.
Wainwright, K.
Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title_full Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title_fullStr Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title_full_unstemmed Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title_short Metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
title_sort metal ion-activated molecular receptors for aromatic anions with receptor cavities formed from 1- or 2-naphthyloxy moieties appended to cyclen
topic Exponent basis-sets
Potentiometric titration
Nuclear-magnetic-resonance
Compact effective potentials
Atoms
Efficient
Inclusion chemistry
Ethers
url http://hdl.handle.net/20.500.11937/26619