Photooxidation of a conjugated diene by an exciplex mechanism: Amplification via radical chain reactions in the perylene diimide-photosensitized oxidation of {alpha}-terpinene
- Univ. of Rochester, NY (United States)
- Eastern Mediterranean Univ., N. Cyprus (Turkey). Dept. of Chemistry
- Ege Univ., Izmir (Turkey). Dept. of Chemistry
Irradiation of the perylene diimide (1) or 9,10-dicyanoanthracene (DCA) in the presence of {alpha}-terpinene (2-HH) in the presence of molecular oxygen leads to moderately efficient oxidation of 2-HH to p-cymene (2). Although 1 might be expected to photosensitize oxidations by the conventional singlet oxygen pathways, spectroscopic studies indicate that while oxygen can quench the fluorescent singlet of 1, no singlet oxygen is produced. 2-HH is also an efficient quencher of the fluorescent singlets of 1 and DCA and, for nonpolar solvents such as methylene chloride, in each case the quenching results in formation of an exciplex or contact radical ion pair. Under conditions where quenching by 2-HH to form the exciplex is complete, maximum quantum yields of 2 are obtained, thus indicating that the exciplex is the precursor to its formation. Nonproductive decay of the exciplex to starting materials is its major fate, thus the moderately high quantum efficiencies for formation of 2 require a mechanism involving amplification. Spin-trapping experiments suggest the role of hydroperoxy radicals and amplification by a radical chain mechanism involving these radicals and the intermediate 2-H{sup {sm_bullet}} is proposed. Possible paths for reaching these radicals from the exciplex are considered; either oxygen quenching of the exciplex or proton transfer within the exciplex followed by oxygen interception of the semireduced perylene diimide appear viable. For the reaction of DCA with 2-HH and oxygen, it is found that the much longer-lived exciplex undergoes quenching by oxygen.
- Sponsoring Organization:
- USDOE, Washington, DC (United States); North Atlantic Treaty Organization, Brussels (Belgium)
- DOE Contract Number:
- FG02-86ER13504
- OSTI ID:
- 316007
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 45 Vol. 102; ISSN 1089-5639; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- English
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