Lakshminarasimhan, PH and Sunoj, RB and Karthikeyan, S and Chandrasekhar, J and Johnston, Linda J and Ramamurthy, V (2002) Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media. In: Journal of Photochemistry and Photobiology A: Chemistry, 153 (1-3). 41-53 .
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The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this article belongs to Elsevier Science.|
|Keywords:||Electron transfer;Geometric isomerization;Stilbene|
|Department/Centre:||Division of Chemical Sciences > Organic Chemistry|
|Date Deposited:||20 Jul 2011 09:19|
|Last Modified:||20 Jul 2011 09:19|
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