An approach to insulated molecular wires: Synthesis of water-soluble conjugated rotaxanes

Sally Anderson, Robin T. Aplin, Tim D W Claridge, Theodore Goodson, Angela C. Maciel, Gary Rumbles, John F. Ryan, Harry L. Anderson

Research output: Contribution to journalArticle

78 Citations (Scopus)

Abstract

Hydrophobic self-assembly has been used to direct the synthesis of conjugated [2] and [3]rotaxanes (20 and 21) in aqueous solution, by Glaser coupling a water-soluble alkyne 3 in the presence of a cyclophane 6. No rotaxanes were formed when cyclodextrins were used instead of the cyclophane. NMR and electrospray mass spectrometry were used to probe the binding properties of the stopper unit 3. NMR ring current shifts and NOEs show that the cyclophane 6 binds mainly to the terminal phenylene unit of 3. In solution cyclodextrins bind less strongly than the cyclophane, whereas in the gas-phase cyclodextrins bind more strongly. The water-soluble rotaxanes are fully characterised by electrospray mass spectrometry, NMR and UV-VIS emission/absorption. Both rotaxanes tend to fragment, by unthreading and by dumbbell-cleavage, during electrospray ionisation, particularly at high cone voltages. The insulation of the conjugated dumbbell inside the [3]rotaxane results in increased fluorescence efficiency. Time-resolved fluorescence measurements show that these rotaxanes decompose during photolysis to give products with longer fluorescence lifetimes; the rate of this photodecomposition is slower for the [3]rotaxane than for the naked dumbbell. The extension of this synthetic approach to larger polyrotaxanes was explored by coupling alkyne 3 and diethynylbenzene 2 in the presence of cyclophane 6; this gives some longer [2] and [3]rotaxanes but higher polyrotaxanes are not formed.

Original languageEnglish
Pages (from-to)2383-2397
Number of pages15
JournalJournal of the Chemical Society - Perkin Transactions 1
Issue number15
Publication statusPublished - Aug 7 1998

Fingerprint

Rotaxanes
Wire
Water
Cyclodextrins
Alkynes
Fluorescence
Nuclear magnetic resonance
Mass spectrometry
Electrospray ionization
Photolysis
Self assembly
Cones
Insulation

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Anderson, S., Aplin, R. T., Claridge, T. D. W., Goodson, T., Maciel, A. C., Rumbles, G., ... Anderson, H. L. (1998). An approach to insulated molecular wires: Synthesis of water-soluble conjugated rotaxanes. Journal of the Chemical Society - Perkin Transactions 1, (15), 2383-2397.

An approach to insulated molecular wires : Synthesis of water-soluble conjugated rotaxanes. / Anderson, Sally; Aplin, Robin T.; Claridge, Tim D W; Goodson, Theodore; Maciel, Angela C.; Rumbles, Gary; Ryan, John F.; Anderson, Harry L.

In: Journal of the Chemical Society - Perkin Transactions 1, No. 15, 07.08.1998, p. 2383-2397.

Research output: Contribution to journalArticle

Anderson, S, Aplin, RT, Claridge, TDW, Goodson, T, Maciel, AC, Rumbles, G, Ryan, JF & Anderson, HL 1998, 'An approach to insulated molecular wires: Synthesis of water-soluble conjugated rotaxanes', Journal of the Chemical Society - Perkin Transactions 1, no. 15, pp. 2383-2397.
Anderson, Sally ; Aplin, Robin T. ; Claridge, Tim D W ; Goodson, Theodore ; Maciel, Angela C. ; Rumbles, Gary ; Ryan, John F. ; Anderson, Harry L. / An approach to insulated molecular wires : Synthesis of water-soluble conjugated rotaxanes. In: Journal of the Chemical Society - Perkin Transactions 1. 1998 ; No. 15. pp. 2383-2397.
@article{60ba6a0784b64286a55a1db848f9eed9,
title = "An approach to insulated molecular wires: Synthesis of water-soluble conjugated rotaxanes",
abstract = "Hydrophobic self-assembly has been used to direct the synthesis of conjugated [2] and [3]rotaxanes (20 and 21) in aqueous solution, by Glaser coupling a water-soluble alkyne 3 in the presence of a cyclophane 6. No rotaxanes were formed when cyclodextrins were used instead of the cyclophane. NMR and electrospray mass spectrometry were used to probe the binding properties of the stopper unit 3. NMR ring current shifts and NOEs show that the cyclophane 6 binds mainly to the terminal phenylene unit of 3. In solution cyclodextrins bind less strongly than the cyclophane, whereas in the gas-phase cyclodextrins bind more strongly. The water-soluble rotaxanes are fully characterised by electrospray mass spectrometry, NMR and UV-VIS emission/absorption. Both rotaxanes tend to fragment, by unthreading and by dumbbell-cleavage, during electrospray ionisation, particularly at high cone voltages. The insulation of the conjugated dumbbell inside the [3]rotaxane results in increased fluorescence efficiency. Time-resolved fluorescence measurements show that these rotaxanes decompose during photolysis to give products with longer fluorescence lifetimes; the rate of this photodecomposition is slower for the [3]rotaxane than for the naked dumbbell. The extension of this synthetic approach to larger polyrotaxanes was explored by coupling alkyne 3 and diethynylbenzene 2 in the presence of cyclophane 6; this gives some longer [2] and [3]rotaxanes but higher polyrotaxanes are not formed.",
author = "Sally Anderson and Aplin, {Robin T.} and Claridge, {Tim D W} and Theodore Goodson and Maciel, {Angela C.} and Gary Rumbles and Ryan, {John F.} and Anderson, {Harry L.}",
year = "1998",
month = "8",
day = "7",
language = "English",
pages = "2383--2397",
journal = "Journal of the Chemical Society, Perkin Transactions 1",
issn = "1470-4358",
publisher = "Chemical Society",
number = "15",

}

TY - JOUR

T1 - An approach to insulated molecular wires

T2 - Synthesis of water-soluble conjugated rotaxanes

AU - Anderson, Sally

AU - Aplin, Robin T.

AU - Claridge, Tim D W

AU - Goodson, Theodore

AU - Maciel, Angela C.

AU - Rumbles, Gary

AU - Ryan, John F.

AU - Anderson, Harry L.

PY - 1998/8/7

Y1 - 1998/8/7

N2 - Hydrophobic self-assembly has been used to direct the synthesis of conjugated [2] and [3]rotaxanes (20 and 21) in aqueous solution, by Glaser coupling a water-soluble alkyne 3 in the presence of a cyclophane 6. No rotaxanes were formed when cyclodextrins were used instead of the cyclophane. NMR and electrospray mass spectrometry were used to probe the binding properties of the stopper unit 3. NMR ring current shifts and NOEs show that the cyclophane 6 binds mainly to the terminal phenylene unit of 3. In solution cyclodextrins bind less strongly than the cyclophane, whereas in the gas-phase cyclodextrins bind more strongly. The water-soluble rotaxanes are fully characterised by electrospray mass spectrometry, NMR and UV-VIS emission/absorption. Both rotaxanes tend to fragment, by unthreading and by dumbbell-cleavage, during electrospray ionisation, particularly at high cone voltages. The insulation of the conjugated dumbbell inside the [3]rotaxane results in increased fluorescence efficiency. Time-resolved fluorescence measurements show that these rotaxanes decompose during photolysis to give products with longer fluorescence lifetimes; the rate of this photodecomposition is slower for the [3]rotaxane than for the naked dumbbell. The extension of this synthetic approach to larger polyrotaxanes was explored by coupling alkyne 3 and diethynylbenzene 2 in the presence of cyclophane 6; this gives some longer [2] and [3]rotaxanes but higher polyrotaxanes are not formed.

AB - Hydrophobic self-assembly has been used to direct the synthesis of conjugated [2] and [3]rotaxanes (20 and 21) in aqueous solution, by Glaser coupling a water-soluble alkyne 3 in the presence of a cyclophane 6. No rotaxanes were formed when cyclodextrins were used instead of the cyclophane. NMR and electrospray mass spectrometry were used to probe the binding properties of the stopper unit 3. NMR ring current shifts and NOEs show that the cyclophane 6 binds mainly to the terminal phenylene unit of 3. In solution cyclodextrins bind less strongly than the cyclophane, whereas in the gas-phase cyclodextrins bind more strongly. The water-soluble rotaxanes are fully characterised by electrospray mass spectrometry, NMR and UV-VIS emission/absorption. Both rotaxanes tend to fragment, by unthreading and by dumbbell-cleavage, during electrospray ionisation, particularly at high cone voltages. The insulation of the conjugated dumbbell inside the [3]rotaxane results in increased fluorescence efficiency. Time-resolved fluorescence measurements show that these rotaxanes decompose during photolysis to give products with longer fluorescence lifetimes; the rate of this photodecomposition is slower for the [3]rotaxane than for the naked dumbbell. The extension of this synthetic approach to larger polyrotaxanes was explored by coupling alkyne 3 and diethynylbenzene 2 in the presence of cyclophane 6; this gives some longer [2] and [3]rotaxanes but higher polyrotaxanes are not formed.

UR - http://www.scopus.com/inward/record.url?scp=33748733806&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33748733806&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:33748733806

SP - 2383

EP - 2397

JO - Journal of the Chemical Society, Perkin Transactions 1

JF - Journal of the Chemical Society, Perkin Transactions 1

SN - 1470-4358

IS - 15

ER -