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Azobenzene Photoisomerization Under High External Pressures: Testing the Strength of a Light-Activated Molecular Muscle

Azobenzene Photoisomerization Under High External Pressures: Testing the Strength of a Light-Activated Molecular Muscle

Thomas A Singleton, Kevin S Ramsay, Mirela M Barsan, Ian S Butler, Christopher J Barrett

J Phys Chem B. 2012 Aug 16;116(32):9860-5.

PMID: 22799454

Abstract:

The photoinduced isomerization and thermal back relaxation of an azobenzene-functionalized polymer poly(disperse red 1 acrylate) were investigated at increasing external pressures up to 1.5 GPa inside a diamond-anvil spectroscopic cell. The thermal cis-trans isomerization was monitored by laser pump-probe spectroscopy, which demonstrated an increase in the half-life of the isomerization process with increasing pressure. Additionally, the cis content of the photostationary state gradually decreased as a function of pressure, with complete arrest of the trans-cis photoisomerization above 1.5 GPa. The fact that the photoswitching behavior however could still be observed beyond 1 GPa is remarkable and is effectively a measure of the strength of the azobenzene chromophore as an artificial muscle. The changes in the Raman shifts of both trans- and cis-azobenzene were also investigated from ambient pressure up to 4 GPa, and no discontinuities were observed in the pressure vs wavenumber plots indicating no change in phase. The cis-trans photoisomerization of azobenzene was shown however to still be inducible at all the pressures investigated, confirming the suitability of these molecules for high-efficiency light actuation.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13695460	Disperse Red 1 acrylate		13695-46-0	Price
AP139427104	Poly(Disperse Red 1 acrylate)		139427-10-4	Price

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