Excited photooxidized

Photochemical oxidation of square-planar bis(l,2-dithiolene) complexes of Ni, Pd, and Pt is by no means limited to IPCT excitation. Photooxidation also occurs in halocarbon solvents. In 1982, two separate reports addressed the photochemistry of metal bis(l,2-dithiolene) complexes. Vogler and Kunkely (80) investigated complexes of the type M(S2C2R-2)2, where M = Ni, Pd, Pt,... 

Generally, photooxidation has an even stronger negative effect on lasing and stimulated emission in conjugated polymers than it has on the EL-performance. It not only reduces the number of excited 5j states but additionally creates charged absorbing species that partly compensate the stimulated emission due to the neutral excited states. 

Significant stimulated emission is only found for the pristine side of the sample. From these results it was concluded that the photoinduccd absorption that suppresses die stimulated emission is directly or indirectly caused by the presence of oxygen-related defects. It was shown earlier that the effect of photooxidation on the emission properties of PPV can be explained by the formation of carbonyl-groups that act as sLrong electron acceptors leading to an efficient dissociation of the plioh excited slate 29). It can be concluded that the dissociated pair near the defcci leads to the strong photoinduccd absorption. The observation that... 

Photolysis reactions often are associated with oxidation because the latter category of reactions frequently can be initiated by light. The photooxidation of phenothiazines with the formation of N- and S-oxides is typical. But photolysis reactions are not restricted to oxidation. In the case of sodium nitroprusside, it is believed that degradation results from loss of the nitro-ligand from the molecule, followed by electronic rearrangement and hydration. Photo-induced reactions are common in steroids [36] an example is the formation of 2-benzoylcholestan-3-one following irradiation of cholest-2-en-3-ol benzoate. Photoadditions of water and of alcohols to the electronically excited state of steroids have also been observed [37],... 

Deoxycytidine (dCyd) (14 in Scheme 2) is also an excellent target for one-electron oxidation reactions mediated by triplet excited menadione. On the basis of extensive identification of dCyd photooxidation products, it was concluded that this nucleoside decomposes by competitive hydration and deprotonation reactions of cytosine radical cations with yields of 52% and 40%, respectively [53]. It was also found, on the basis of 180 labeling experiments, that hydration of cytosine radical cations (15) predominantly occurs... 

Clearly all the answers to the questions of the mechanisms of both the photodimerization and photooxidation of anthracene are not yet known. Hopefully, what we have seen in this chapter will serve to convince the reader that photochemistry is still an exciting and challenging field of study in which there is ample room for further research. 

Jeevarajan, A. S., L. D. Kispert et al. (1996b). Role of excited singlet state in the photooxidation of carotenoids a time resolved Q-band EPR study. J. Phys. Chem. 100 669-671. 

On the other hand, carbonyl quenching by polyenyl radicals in PVC has been invoked in order to account for autoinhibition during photooxidative degradation (52). Some workers have mentioned the possibility of singlet oxygen formation in PVC via the quenching of excited polyenes (25,29) or cyclohexadienes (53). 

Fluorescence Analysis of Irradiated PET and PET-co-4,4 -BPDC Yarns. The presence of a material, which emits a blue-green fluorescence, on photooxidized PET has been reported previously (2, 21). This fluorescent material, which emits at 460 nm when excited by 342 nm energy, has been proved to be monohydroxy-tere-phthalate. 

Figure 3 Type I and type II photooxidation processes with a porphyrin sensitizer illustrated with a modified Jablonski diagram. (S0 = ground singlet state, Si = first excited singlet state, S2 = second excited singlet state, T,i— ground triplet state, Ti = first excited triplet state, i.s.c. — intersystem crossing.)...

Gray [215] studied the photooxidation of methane and ethane at room temperature in the gas phase using Hg as a photosensitizer. Hydroperoxide was found as the product of oxidation. Along with hydroperoxide, ozone was also found as the product of photooxidation. It was supposed to be due to the reaction of excited mercury atoms with dioxygen. 

The acyl radicals formed in ketone photolysis are excited and, therefore, rapidly splits into CO and alkyl radical (in the gas phase). Since aldehydes and ketones are products of oxidation, continuous hydrocarbon photooxidation is an autoaccelerated process. 

In a number of cases ITIES can be used to separate the products of a photoinduced electron-transfer reaction. An early example is the work by Willner et al. [7] at the water/toluene interface, who studied the photooxidation of [Ru(bpy)3]2+ in the aqueous phase. The excited state was quenched by hexadecyl- 4,4 bipyridinium, which becomes hydrophobic on reduction and crosses to the toluene phase. There are other examples and mechanisms at the present time their main interest resides in their chemistry, and in the separation of products that can be achieved at the interface. 

The photo-oxidation of the aryl-substituted cycloheptatrienes 7-(/ -methoxy-phenyl)cycloheptatriene and 7-, 1- and 3-(/ -dimethylaminophenyl)cycloheptatrienes to the corresponding radical cations in de-aerated acetonitrile solution was accomplished by electron transfer to the electronically excited acceptors 9,10-dicyanoanthracene, iV-methylquinolinium perchlorate, iV-methylacridinium perchlorate and l,T-dimethyl-4,4-bipyridinium dichloride. In the case of l- p-methoxyphenyl)cycloheptatriene (62), deprotonation of the radical cation occurs successfully, compared with back electron transfer, to give a cycloheptatrienyl radical (63) which undergoes a self-reaction forming a bitropyl. If the photooxidation is done in air-saturated acetonitrile solution containing HBF4 and one of the acceptors, the tropylium cation is formed. Back electron transfer dominates in the / -dimethylaminocycloheptatrienes and the formation of the cycloheptatrienyl radical is prevented. 

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