Optical and chiroptical switches based on photoinduced photon and proton transfer in copolymers containing spiropyran and azopyridine chromophores in their side chains

L. Angiolini, T. Benelli, L. Giorgini, Francisco Raymo

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

New methacrylic copolymers, bearing in the side chain spiropyran moieties and/or the optically-active (S)-3-hydroxy pyrrolidinyl group linked through the nitrogen atom to an azopyridine chromophore, along with an opportune molar content of methyl methacrylate co-units, have been prepared by radical polymerization of the corresponding monomers. The resulting macromolecules have been fully characterized with particular attention to the study of their thermal stability, optical activity, chiroptical and photoinduced properties. In the presence of acid, it is possible to modulate the protonation of the azopyridine groups by photo-isomerization (with UV and/or Vis light) of the spiropyran component. The resulting signal communication between these macromolecular switches can be monitored by UV-VIS as well as CD spectroscopy and is completely reversible and reproducible. The results are discussed in terms of copolymer composition and different cooperative behaviour, which lead to a variation of interactions between spiropyran and azoaromatic chromophores and reveal that the best proton transfer is actually obtained in the random terpolymer with lower amounts of co-units of spiropyran and azopyridine chromophores in the side chain, which displays improved sensitivity to proton-transfer process and, in addition, exhibits good stability to repeated cycles of irradiation with UV and Vis light.

Original languageEnglish
Pages (from-to)5638-5646
Number of pages9
JournalPolymer
Volume50
Issue number24
DOIs
StatePublished - Nov 16 2009

Fingerprint

Proton transfer
Chromophores
Photons
Copolymers
Switches
Bearings (structural)
Photoisomerization
Terpolymers
Protonation
Free radical polymerization
Macromolecules
Methacrylates
Thermodynamic stability
Monomers
Irradiation
Spectroscopy
Nitrogen
Atoms
Acids
Communication

Keywords

  • Azopyridine
  • Polymeric chiroptical switches
  • Spiropyran

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics

Cite this

Optical and chiroptical switches based on photoinduced photon and proton transfer in copolymers containing spiropyran and azopyridine chromophores in their side chains. / Angiolini, L.; Benelli, T.; Giorgini, L.; Raymo, Francisco.

In: Polymer, Vol. 50, No. 24, 16.11.2009, p. 5638-5646.

Research output: Contribution to journalArticle

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AU - Giorgini, L.

AU - Raymo, Francisco

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AB - New methacrylic copolymers, bearing in the side chain spiropyran moieties and/or the optically-active (S)-3-hydroxy pyrrolidinyl group linked through the nitrogen atom to an azopyridine chromophore, along with an opportune molar content of methyl methacrylate co-units, have been prepared by radical polymerization of the corresponding monomers. The resulting macromolecules have been fully characterized with particular attention to the study of their thermal stability, optical activity, chiroptical and photoinduced properties. In the presence of acid, it is possible to modulate the protonation of the azopyridine groups by photo-isomerization (with UV and/or Vis light) of the spiropyran component. The resulting signal communication between these macromolecular switches can be monitored by UV-VIS as well as CD spectroscopy and is completely reversible and reproducible. The results are discussed in terms of copolymer composition and different cooperative behaviour, which lead to a variation of interactions between spiropyran and azoaromatic chromophores and reveal that the best proton transfer is actually obtained in the random terpolymer with lower amounts of co-units of spiropyran and azopyridine chromophores in the side chain, which displays improved sensitivity to proton-transfer process and, in addition, exhibits good stability to repeated cycles of irradiation with UV and Vis light.

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