Photooxidation of a conjugated diene by an exciplex mechanism: Amplification via radical chain reactions in the perylene diimide-photosensitized oxidation of alpha-terpinene
Küçük Resim Yok
Tarih
1998
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Amer Chemical Soc
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
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-. 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.
Açıklama
Anahtar Kelimeler
Kaynak
Journal of Physical Chemistry A
WoS Q Değeri
Q2
Scopus Q Değeri
Cilt
102
Sayı
45
