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 x 10(-1) 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)(3)CH 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 zoolite 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)(3)O could be generated from P(C6H5)(3) in aerated CH3CN. If AgF was added, the major product shifted from P(C6H5)(3)O to P(C6H5)(3)F-2. Under a similar photolysis condition, (C6H5)(3)CF was the major derivative of triphenylmethane. These results suggested that P(C6H5)(3)(+), P(C6H5)(3)(2+), and (C6H5)(3)C+ had been generated. Electron transfer reaction was evidenced to play a key role in the NaY/Fe2+/DCA- and NaY/Fe2+/CA-sensitized photoreactions.