Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds

Masumi Asakawa, Peter R. Ashton, Vincenzo Balzani, Christopher L. Brown, Alberto Credi, Owen A. Matthews, Simon P. Newton, Francisco Raymo, Andrew N. Shipway, Neil Spencer, Andrew Quick, J. Fraser Stoddart, Andrew J P White, David J. Williams

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

Two acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4′-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene) - a tetracationic cyclophane - in their trans forms only. On irradiation (λ = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4′-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (λ = 440 nm) or by warming the solution in the dark. Variable temperature 1H NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4′-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4′-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (λ = 360 nm) from the trans to the cis isomer of the 4,4′-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4′-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.

Original languageEnglish
Pages (from-to)860-875
Number of pages16
JournalChemistry - A European Journal
Volume5
Issue number3
StatePublished - Dec 1 1999
Externally publishedYes

Fingerprint

Catenanes
Azobenzene
Polyethers
Rotaxanes
Isomers
Photoisomerization
Fluorescence
Irradiation
Isomerization
Structural analysis
Energy transfer
Quenching
Paraquat
Nuclear magnetic resonance
Single crystals
X rays
Crystals
azobenzene

Keywords

  • Catenanes
  • Molecular devices
  • Molecular recognition
  • Rotaxanes
  • Template synthesis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Asakawa, M., Ashton, P. R., Balzani, V., Brown, C. L., Credi, A., Matthews, O. A., ... Williams, D. J. (1999). Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds. Chemistry - A European Journal, 5(3), 860-875.

Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds. / Asakawa, Masumi; Ashton, Peter R.; Balzani, Vincenzo; Brown, Christopher L.; Credi, Alberto; Matthews, Owen A.; Newton, Simon P.; Raymo, Francisco; Shipway, Andrew N.; Spencer, Neil; Quick, Andrew; Stoddart, J. Fraser; White, Andrew J P; Williams, David J.

In: Chemistry - A European Journal, Vol. 5, No. 3, 01.12.1999, p. 860-875.

Research output: Contribution to journalArticle

Asakawa, M, Ashton, PR, Balzani, V, Brown, CL, Credi, A, Matthews, OA, Newton, SP, Raymo, F, Shipway, AN, Spencer, N, Quick, A, Stoddart, JF, White, AJP & Williams, DJ 1999, 'Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds', Chemistry - A European Journal, vol. 5, no. 3, pp. 860-875.
Asakawa M, Ashton PR, Balzani V, Brown CL, Credi A, Matthews OA et al. Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds. Chemistry - A European Journal. 1999 Dec 1;5(3):860-875.
Asakawa, Masumi ; Ashton, Peter R. ; Balzani, Vincenzo ; Brown, Christopher L. ; Credi, Alberto ; Matthews, Owen A. ; Newton, Simon P. ; Raymo, Francisco ; Shipway, Andrew N. ; Spencer, Neil ; Quick, Andrew ; Stoddart, J. Fraser ; White, Andrew J P ; Williams, David J. / Photoactive azobenzene-containing supramolecular complexes and related interlocked molecular compounds. In: Chemistry - A European Journal. 1999 ; Vol. 5, No. 3. pp. 860-875.
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AU - Asakawa, Masumi

AU - Ashton, Peter R.

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AU - Credi, Alberto

AU - Matthews, Owen A.

AU - Newton, Simon P.

AU - Raymo, Francisco

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AB - Two acyclic and three macrocyclic polyethers, three [2]catenanes, and one [2]rotaxane, each containing one 4,4′-azobiphenoxy unit, have been synthesized. In solution, the azobenzene-based acyclic polyethers are bound by cyclobis(paraquat-p-phenylene) - a tetracationic cyclophane - in their trans forms only. On irradiation (λ = 360 nm) of an equimolar solution of the tetracationic cyclophane host and one of the guests containing a trans-4,4′-azobiphenoxy unit, the trans double bond isomerizes to its cis form and the supramolecular complex dissociates into its molecular components. The trans isomer of the guest and, as a result, the complex are reformed, either by irradiation (λ = 440 nm) or by warming the solution in the dark. Variable temperature 1H NMR spectroscopic investigations of the [2]catenanes and the [2]rotaxane revealed that, in all cases, the 4,4′-azobiphenoxy unit resides preferentially alongside the cavities of their tetracationic cyclophane components, which are occupied either by a 1,4-dioxybenzene or by a 1,5-dioxynaphthalene unit. In the acyclic and macrocyclic polyethers containing 1,4-dioxybenzene or 1,5-dioxynaphthalene chromophoric groups and a 4,4′-azobiphenoxy moiety, the fluorescence of the former units is quenched by the latter. Fluorescence quenching is accompanied by photosensitization of the isomerization. The rate of the energy-transfer process is different for trans and cis isomers. In the [2]rotaxane and the [2]catenanes, the photoisomerization is quenched to an extent that depends on the specific structure of the compound. Only in one of the three [2]catenanes and in the [2]rotaxane was an efficient photoisomerization (λ = 360 nm) from the trans to the cis isomer of the 4,4′-azobiphenoxy unit observed. Single crystal X-ray structural analysis of one of the [2]catenanes showed that, in the solid state, the 4,4′-azobiphenoxy unit in the macrocyclic polyether component also resides exclusively alongside. The cavity of the tetracationic cyclophane component of the [2]catenane is filled by a 1,5-dioxynaphthalene unit, and infinite donor-acceptor stacks between adjacent [2]catenanes are formed in the crystal. These supramolecular complexes and their mechanically interlocked molecular counterparts can be regarded as potential photoactive nanoscale devices.

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KW - Molecular devices

KW - Molecular recognition

KW - Rotaxanes

KW - Template synthesis

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