Energetic probing for the electron transfer reactions sensitized by 9,10-dicyanoanthracene and 9-cyanoanthracene and their modified zeolite particles

Yu Chen Chang, Pei Wen Chang, Chong Mou Wang

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The photooxidation of diphenylamine (DPA) and triphenylphosphine (P(C6H5)3) sensitized by 9,10-dicyanoanthracene (DCA) and 9-cyanoanthracene (CA) was investigated in this work. Theoretically and evidently, DPA could quench the excited DCA and CA (denoted DCA* and CA*) via an electron transfer pathway. The Stern-Volmer quenching rate constants were calculated to be ca. 4 × 104 equiv-1 s-1 for both DCA* and CA*. In contrast to DPA, P(C6H5)3 showed no quenching effects on DCA* and CA* and only P(C6H5)3 was excited along with the sensitizers upon the exposure to UV light (260 nm). The formal potentials of DCA*/- and CA*/- were thus concluded to be located between the formal potentials of DPA+/0 (1.5 V vs SCE) and the formal potentials of P(C6H5)3+/0 (ca. 2 V vs SCE). Oxygen could significantly quench DCA* and CA* via an energy transfer pathway. Photooxygenations of P(C6H5)3 and (C6H5)3CH were carried out using the DCA- and CA-exchanged zeolite particles (denoted NaY/DCA and NaY/CA) as the heterogeneous catalysts. Noticeably, as DCA and CA were adsorbed on the zeolite particles, their excited states became longer-lived (ca. 100 ns) as compared to the solution counterparts (ca. 13 ns under nitrogen), which also caused a severe retardation to the electron transfer between the electron donors outside the zeolite particles and the DCA*(NaY) and CA*(NaY). Iron(II) ions could activate these retarded photoinduced electron transfer reactions. Under the photocatalysis of the NaY/Fe2+/DCA particle, P(C6H5)3O could be generated from P(C6H5)3 in aerated CH3CN. If AgF was added, the major product shifted from P(C6H5)3O to P(C6H5)3F2. Under a similar photolysis condition, (C6H5)3CF was the major derivative of triphenylmethane. These results suggested that P(C6H5)3+, P(C6H5)32+, and (C6H5)3C+ had been generated. Electron transfer reaction was evidenced to play a key role in the NaY/Fe2+/DCA- and NaY/Fe2+/CA-sensitized photoreactions.

Original languageEnglish
Pages (from-to)1628-1633
Number of pages6
JournalJournal of Physical Chemistry B
Volume107
Issue number7
DOIs
Publication statusPublished - 2003 Feb 20

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Zeolites
Diphenylamine
electron transfer
Electrons
quenching
Quenching
photooxidation
Photooxidation
Photocatalysis
Photolysis
Energy Transfer
photolysis
Ultraviolet Rays
Excited states
Ultraviolet radiation
Energy transfer
energy transfer
Rate constants
iron
nitrogen

ASJC Scopus subject areas

  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Energetic probing for the electron transfer reactions sensitized by 9,10-dicyanoanthracene and 9-cyanoanthracene and their modified zeolite particles. / Chang, Yu Chen; Chang, Pei Wen; Wang, Chong Mou.

In: Journal of Physical Chemistry B, Vol. 107, No. 7, 20.02.2003, p. 1628-1633.

Research output: Contribution to journalArticle

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abstract = "The photooxidation of diphenylamine (DPA) and triphenylphosphine (P(C6H5)3) sensitized by 9,10-dicyanoanthracene (DCA) and 9-cyanoanthracene (CA) was investigated in this work. Theoretically and evidently, DPA could quench the excited DCA and CA (denoted DCA* and CA*) via an electron transfer pathway. The Stern-Volmer quenching rate constants were calculated to be ca. 4 × 104 equiv-1 s-1 for both DCA* and CA*. In contrast to DPA, P(C6H5)3 showed no quenching effects on DCA* and CA* and only P(C6H5)3 was excited along with the sensitizers upon the exposure to UV light (260 nm). The formal potentials of DCA*/- and CA*/- were thus concluded to be located between the formal potentials of DPA+/0 (1.5 V vs SCE) and the formal potentials of P(C6H5)3+/0 (ca. 2 V vs SCE). Oxygen could significantly quench DCA* and CA* via an energy transfer pathway. Photooxygenations of P(C6H5)3 and (C6H5)3CH were carried out using the DCA- and CA-exchanged zeolite particles (denoted NaY/DCA and NaY/CA) as the heterogeneous catalysts. Noticeably, as DCA and CA were adsorbed on the zeolite particles, their excited states became longer-lived (ca. 100 ns) as compared to the solution counterparts (ca. 13 ns under nitrogen), which also caused a severe retardation to the electron transfer between the electron donors outside the zeolite particles and the DCA*(NaY) and CA*(NaY). Iron(II) ions could activate these retarded photoinduced electron transfer reactions. Under the photocatalysis of the NaY/Fe2+/DCA particle, P(C6H5)3O could be generated from P(C6H5)3 in aerated CH3CN. If AgF was added, the major product shifted from P(C6H5)3O to P(C6H5)3F2. Under a similar photolysis condition, (C6H5)3CF was the major derivative of triphenylmethane. These results suggested that P(C6H5)3+, P(C6H5)32+, and (C6H5)3C+ had been generated. Electron transfer reaction was evidenced to play a key role in the NaY/Fe2+/DCA- and NaY/Fe2+/CA-sensitized photoreactions.",
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N2 - The photooxidation of diphenylamine (DPA) and triphenylphosphine (P(C6H5)3) sensitized by 9,10-dicyanoanthracene (DCA) and 9-cyanoanthracene (CA) was investigated in this work. Theoretically and evidently, DPA could quench the excited DCA and CA (denoted DCA* and CA*) via an electron transfer pathway. The Stern-Volmer quenching rate constants were calculated to be ca. 4 × 104 equiv-1 s-1 for both DCA* and CA*. In contrast to DPA, P(C6H5)3 showed no quenching effects on DCA* and CA* and only P(C6H5)3 was excited along with the sensitizers upon the exposure to UV light (260 nm). The formal potentials of DCA*/- and CA*/- were thus concluded to be located between the formal potentials of DPA+/0 (1.5 V vs SCE) and the formal potentials of P(C6H5)3+/0 (ca. 2 V vs SCE). Oxygen could significantly quench DCA* and CA* via an energy transfer pathway. Photooxygenations of P(C6H5)3 and (C6H5)3CH were carried out using the DCA- and CA-exchanged zeolite particles (denoted NaY/DCA and NaY/CA) as the heterogeneous catalysts. Noticeably, as DCA and CA were adsorbed on the zeolite particles, their excited states became longer-lived (ca. 100 ns) as compared to the solution counterparts (ca. 13 ns under nitrogen), which also caused a severe retardation to the electron transfer between the electron donors outside the zeolite particles and the DCA*(NaY) and CA*(NaY). Iron(II) ions could activate these retarded photoinduced electron transfer reactions. Under the photocatalysis of the NaY/Fe2+/DCA particle, P(C6H5)3O could be generated from P(C6H5)3 in aerated CH3CN. If AgF was added, the major product shifted from P(C6H5)3O to P(C6H5)3F2. Under a similar photolysis condition, (C6H5)3CF was the major derivative of triphenylmethane. These results suggested that P(C6H5)3+, P(C6H5)32+, and (C6H5)3C+ had been generated. Electron transfer reaction was evidenced to play a key role in the NaY/Fe2+/DCA- and NaY/Fe2+/CA-sensitized photoreactions.

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