Pseudorotaxanes and rotaxanes formed by viologen derivatives

Adam Braunschweig, Célia M. Ronconi, Ja Young Han, Fabio Aricó, Stuart J. Cantrill, J. Fraser Stoddart, Saeed I. Khan, Andrew J P White, David J. Williams

Research output: Contribution to journalArticle

48 Citations (Scopus)

Abstract

Dibenzyl-4,4′-bipyridinium (BIPY2+) bis(hexafluorophosphate) and three of its derivatives - disubstituted at the para positions of the benzyl groups with CO2Me, F, and Me in turn - have been shown to form 1:1 complexes that are [2]pseudorotaxanes with dibenzo[24]crown-8 (DB24C8), benzometaphenylene[25]crown-8 (BMP25C8), and dipyrido[24]crown-8 (DP24C8) in CD3CN solution by 1H NMR spectroscopy and in one case in the solid state by X-ray crystallography. Binding constants (Ka) for all of these 1:1 complexes, which were determined both (1) by isothermal titration calorimetry in MeCN solution and (2) by the 1H NMR spectroscopic single-point method in CD3CN solution, were found to be, on the average, an order of magnitude less than the Ka values obtained for DB24C8 and DP24C8 with dibenzylammonium (DBA+) hexafluorophosphate and three of its derivatives, also disubstituted at the para positions of the benzyl groups with CO2Me, F and Me. In the case of BMP25C8, however, the Ka values with both categories (BIPY2+ and DBA+) of guests are much of a muchness, being both small and error prone. The equilibrium thermodynamics for these small libraries of [2]pseudorotaxanes indicate that the best bistable [2]rotaxanes incorporating both DBA+ and BIPY2+ recognition sites are going to involve ester functions in their dumbbell components and will employ DP24C8 or, failing that, DB24C8 as the ring component. The BIPY2+ threads also directed the templated assembly of [2]rotaxanes incorporating the crown ethers (DB24C8, DP24C8, and BMP25C8) and triphenylphosphonium stoppers using the threading followed by stoppering approach. The rotaxanes were characterized in solution by 1H NMR spectroscopy, and in one case, in the solid state by X-ray crystallography.

Original languageEnglish (US)
Pages (from-to)1857-1866
Number of pages10
JournalEuropean Journal of Organic Chemistry
Issue number8
DOIs
StatePublished - Apr 10 2006
Externally publishedYes

Fingerprint

Viologens
Rotaxanes
Derivatives
nuclear magnetic resonance
crystallography
solid state
threads
X ray crystallography
thermodynamic equilibrium
titration
spectroscopy
Nuclear magnetic resonance spectroscopy
esters
ethers
x rays
heat measurement
assembly
Crown Ethers
rings
Calorimetry

Keywords

  • [2]Rotaxanes
  • Host-guest system
  • Isothermal titration microcalorimetry
  • Nanotechnology
  • Noncovalent interactions

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Braunschweig, A., Ronconi, C. M., Han, J. Y., Aricó, F., Cantrill, S. J., Stoddart, J. F., ... Williams, D. J. (2006). Pseudorotaxanes and rotaxanes formed by viologen derivatives. European Journal of Organic Chemistry, (8), 1857-1866. https://doi.org/10.1002/ejoc.200500947

Pseudorotaxanes and rotaxanes formed by viologen derivatives. / Braunschweig, Adam; Ronconi, Célia M.; Han, Ja Young; Aricó, Fabio; Cantrill, Stuart J.; Stoddart, J. Fraser; Khan, Saeed I.; White, Andrew J P; Williams, David J.

In: European Journal of Organic Chemistry, No. 8, 10.04.2006, p. 1857-1866.

Research output: Contribution to journalArticle

Braunschweig, A, Ronconi, CM, Han, JY, Aricó, F, Cantrill, SJ, Stoddart, JF, Khan, SI, White, AJP & Williams, DJ 2006, 'Pseudorotaxanes and rotaxanes formed by viologen derivatives', European Journal of Organic Chemistry, no. 8, pp. 1857-1866. https://doi.org/10.1002/ejoc.200500947
Braunschweig A, Ronconi CM, Han JY, Aricó F, Cantrill SJ, Stoddart JF et al. Pseudorotaxanes and rotaxanes formed by viologen derivatives. European Journal of Organic Chemistry. 2006 Apr 10;(8):1857-1866. https://doi.org/10.1002/ejoc.200500947
Braunschweig, Adam ; Ronconi, Célia M. ; Han, Ja Young ; Aricó, Fabio ; Cantrill, Stuart J. ; Stoddart, J. Fraser ; Khan, Saeed I. ; White, Andrew J P ; Williams, David J. / Pseudorotaxanes and rotaxanes formed by viologen derivatives. In: European Journal of Organic Chemistry. 2006 ; No. 8. pp. 1857-1866.
@article{7efe98f58caf402aa8c4593538ad434e,
title = "Pseudorotaxanes and rotaxanes formed by viologen derivatives",
abstract = "Dibenzyl-4,4′-bipyridinium (BIPY2+) bis(hexafluorophosphate) and three of its derivatives - disubstituted at the para positions of the benzyl groups with CO2Me, F, and Me in turn - have been shown to form 1:1 complexes that are [2]pseudorotaxanes with dibenzo[24]crown-8 (DB24C8), benzometaphenylene[25]crown-8 (BMP25C8), and dipyrido[24]crown-8 (DP24C8) in CD3CN solution by 1H NMR spectroscopy and in one case in the solid state by X-ray crystallography. Binding constants (Ka) for all of these 1:1 complexes, which were determined both (1) by isothermal titration calorimetry in MeCN solution and (2) by the 1H NMR spectroscopic single-point method in CD3CN solution, were found to be, on the average, an order of magnitude less than the Ka values obtained for DB24C8 and DP24C8 with dibenzylammonium (DBA+) hexafluorophosphate and three of its derivatives, also disubstituted at the para positions of the benzyl groups with CO2Me, F and Me. In the case of BMP25C8, however, the Ka values with both categories (BIPY2+ and DBA+) of guests are much of a muchness, being both small and error prone. The equilibrium thermodynamics for these small libraries of [2]pseudorotaxanes indicate that the best bistable [2]rotaxanes incorporating both DBA+ and BIPY2+ recognition sites are going to involve ester functions in their dumbbell components and will employ DP24C8 or, failing that, DB24C8 as the ring component. The BIPY2+ threads also directed the templated assembly of [2]rotaxanes incorporating the crown ethers (DB24C8, DP24C8, and BMP25C8) and triphenylphosphonium stoppers using the threading followed by stoppering approach. The rotaxanes were characterized in solution by 1H NMR spectroscopy, and in one case, in the solid state by X-ray crystallography.",
keywords = "[2]Rotaxanes, Host-guest system, Isothermal titration microcalorimetry, Nanotechnology, Noncovalent interactions",
author = "Adam Braunschweig and Ronconi, {C{\'e}lia M.} and Han, {Ja Young} and Fabio Aric{\'o} and Cantrill, {Stuart J.} and Stoddart, {J. Fraser} and Khan, {Saeed I.} and White, {Andrew J P} and Williams, {David J.}",
year = "2006",
month = "4",
day = "10",
doi = "10.1002/ejoc.200500947",
language = "English (US)",
pages = "1857--1866",
journal = "Annalen der Pharmacie",
issn = "0075-4617",
publisher = "Wiley-VCH Verlag",
number = "8",

}

TY - JOUR

T1 - Pseudorotaxanes and rotaxanes formed by viologen derivatives

AU - Braunschweig, Adam

AU - Ronconi, Célia M.

AU - Han, Ja Young

AU - Aricó, Fabio

AU - Cantrill, Stuart J.

AU - Stoddart, J. Fraser

AU - Khan, Saeed I.

AU - White, Andrew J P

AU - Williams, David J.

PY - 2006/4/10

Y1 - 2006/4/10

N2 - Dibenzyl-4,4′-bipyridinium (BIPY2+) bis(hexafluorophosphate) and three of its derivatives - disubstituted at the para positions of the benzyl groups with CO2Me, F, and Me in turn - have been shown to form 1:1 complexes that are [2]pseudorotaxanes with dibenzo[24]crown-8 (DB24C8), benzometaphenylene[25]crown-8 (BMP25C8), and dipyrido[24]crown-8 (DP24C8) in CD3CN solution by 1H NMR spectroscopy and in one case in the solid state by X-ray crystallography. Binding constants (Ka) for all of these 1:1 complexes, which were determined both (1) by isothermal titration calorimetry in MeCN solution and (2) by the 1H NMR spectroscopic single-point method in CD3CN solution, were found to be, on the average, an order of magnitude less than the Ka values obtained for DB24C8 and DP24C8 with dibenzylammonium (DBA+) hexafluorophosphate and three of its derivatives, also disubstituted at the para positions of the benzyl groups with CO2Me, F and Me. In the case of BMP25C8, however, the Ka values with both categories (BIPY2+ and DBA+) of guests are much of a muchness, being both small and error prone. The equilibrium thermodynamics for these small libraries of [2]pseudorotaxanes indicate that the best bistable [2]rotaxanes incorporating both DBA+ and BIPY2+ recognition sites are going to involve ester functions in their dumbbell components and will employ DP24C8 or, failing that, DB24C8 as the ring component. The BIPY2+ threads also directed the templated assembly of [2]rotaxanes incorporating the crown ethers (DB24C8, DP24C8, and BMP25C8) and triphenylphosphonium stoppers using the threading followed by stoppering approach. The rotaxanes were characterized in solution by 1H NMR spectroscopy, and in one case, in the solid state by X-ray crystallography.

AB - Dibenzyl-4,4′-bipyridinium (BIPY2+) bis(hexafluorophosphate) and three of its derivatives - disubstituted at the para positions of the benzyl groups with CO2Me, F, and Me in turn - have been shown to form 1:1 complexes that are [2]pseudorotaxanes with dibenzo[24]crown-8 (DB24C8), benzometaphenylene[25]crown-8 (BMP25C8), and dipyrido[24]crown-8 (DP24C8) in CD3CN solution by 1H NMR spectroscopy and in one case in the solid state by X-ray crystallography. Binding constants (Ka) for all of these 1:1 complexes, which were determined both (1) by isothermal titration calorimetry in MeCN solution and (2) by the 1H NMR spectroscopic single-point method in CD3CN solution, were found to be, on the average, an order of magnitude less than the Ka values obtained for DB24C8 and DP24C8 with dibenzylammonium (DBA+) hexafluorophosphate and three of its derivatives, also disubstituted at the para positions of the benzyl groups with CO2Me, F and Me. In the case of BMP25C8, however, the Ka values with both categories (BIPY2+ and DBA+) of guests are much of a muchness, being both small and error prone. The equilibrium thermodynamics for these small libraries of [2]pseudorotaxanes indicate that the best bistable [2]rotaxanes incorporating both DBA+ and BIPY2+ recognition sites are going to involve ester functions in their dumbbell components and will employ DP24C8 or, failing that, DB24C8 as the ring component. The BIPY2+ threads also directed the templated assembly of [2]rotaxanes incorporating the crown ethers (DB24C8, DP24C8, and BMP25C8) and triphenylphosphonium stoppers using the threading followed by stoppering approach. The rotaxanes were characterized in solution by 1H NMR spectroscopy, and in one case, in the solid state by X-ray crystallography.

KW - [2]Rotaxanes

KW - Host-guest system

KW - Isothermal titration microcalorimetry

KW - Nanotechnology

KW - Noncovalent interactions

UR - http://www.scopus.com/inward/record.url?scp=33646179087&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33646179087&partnerID=8YFLogxK

U2 - 10.1002/ejoc.200500947

DO - 10.1002/ejoc.200500947

M3 - Article

AN - SCOPUS:33646179087

SP - 1857

EP - 1866

JO - Annalen der Pharmacie

JF - Annalen der Pharmacie

SN - 0075-4617

IS - 8

ER -