Using heavy atom rare gas matrix to control the reactivity of 4-methoxybenzaldehyde: A comparison with benzaldehyde

Kus N., Sharma A., Reva I., Lapinski L., Fausto R.

JOURNAL OF CHEMICAL PHYSICS, vol.136, no.14, 2012 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 136 Issue: 14
  • Publication Date: 2012
  • Doi Number: 10.1063/1.3701734
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Anadolu University Affiliated: Yes


Different patterns of photochemical behavior were observed for 4-methoxybenzaldehyde (p-anisaldehyde) isolated in xenon and in argon matrices. Monomers of the compound isolated in solid Xe decarbonylate upon middle ultraviolet irradiation, yielding methoxybenzene (anisole), and CO. On the other hand, p-anisaldehyde isolated in an Ar matrix and subjected to identical irradiation, predominantly isomerizes to the closed-ring isomeric ketene (4-methoxycyclohexa-2,4-dien-1-ylidene) methanone. Experimental detection of a closed-ring ketene photoproduct, generated from an aromatic aldehyde, constitutes a rare observation. The difference between the patterns of photochemical transformations of p-anisaldehyde isolated in argon and xenon environments can be attributed to the external heavy-atom effect, where xenon enhances the rate of intersystem crossing from the singlet to the triplet manifold in which decarbonylation (via p-methoxybenzoyl radical) takes place. The parent compound, benzaldehyde, decarbonylates (to benzene + CO) when subjected to middle ultraviolet irradiation in both argon and xenon matrices. This demonstrates the role of the methoxy p-anisaldehyde substituent in activation of the reaction channel leading to the formation of the ketene photoproduct. (C) 2012 American Institute of Physics. []