Phenothiazine as donor

The Eisenberg group has been investigating the utility of the Pt(NAN) (-C=C-Ar)2 unit as the central chromophore in such systems. Thus the complex 14 was prepared, incorporating phenothiazine (PTZ) donor groups... 

Argazzi et al. followed that strategy to elaborate a nanocrystalline solar cell which incorporates a molecular dyad (HI) based on ruthenium bipyridine as a sensitizer and phenothiazine as a donor (Figure 19) [109]. 

ESR of paramagnetic free radicals can be used to check the efficacy of AOs and other stabilisers. ESR was used in the study of phenothiazines as antioxidants in PP aromatic secondary amines can retard polymer oxidation by reacting with alkylperoxy radicals [824]. Tkac [825] has described hydrogen and electron transfer reactions of AOs by ESR and has shown the efficiency of the ESR technique in elucidating the relationship between structure and reactivity of radicals formed from antioxidants possessing different H- and e-donor functional groups, including (hindered) phenols, amines, etc. 

It is known from electrochemical studies that fullerenes are easily reduced. Up to 6 electrons can be added reversibly [19], and, as mentioned earlier, the excited states are even more easily reduced. A large number of electron donors were investigated including aromatic and alkyl amines [29,43,79,119-140,152,161], ni-troxide radicals [57,117], suspensions of Ti02 [118], polyaromatic compounds, [19,127] organo-silicon compounds, [133,158] phenothiazine, [133] acridine [145,154], (3-carotene [141], tetrathiafulvalenes [146], tetraethoxyethene [147], phthalocyanines [148], porphyrines [151,153], NADH and analogues [150,154, 155], borates [156,159], and naphtoles [23] to name a few representative cases. 

It is now well established that a variety of organic molecules such as polynuclear aromatic hydrocarbons with low ionization energies act as electron donors with the formation of radical cations when adsorbed on oxide surfaces. Conversely, electron-acceptor molecules with high electron affinity interact with donor sites on oxide surfaces and are converted to anion radicals. These surface species can either be detected by their electronic spectra (90-93, 308-310) or by ESR. The ESR results have recently been reviewed by Flockhart (311). Radical cation-producing substances have only scarcely been applied as poisons in catalytic reactions. Conclusions on the nature of catalytically active sites have preferentially been drawn by qualitative comparison of the surface spin concentration and the catalytic activity as a function of, for example, the pretreatment temperature of the catalyst. Only phenothiazine has been used as a specific poison for the butene-1 isomerization on alumina [Ghorbel et al. (312)). Tetra-cyaonoethylene, on the contrary, has found wide application as a poison during catalytic reactions for the detection of active sites with basic or electron-donor character. This is probably due to the lack of other suitable acidic probe or poison molecules. 

Various compounds were shown to sensitize the photochemical decomposition of pyridinium salts. Photolysis of pyridinium salts in the presence of sensitizers such as anthracene, perylene and phenothiazine proceeds by an electron transfer from the excited state sensitizer to the pyridinium salt. Thus, a sensitizer radical cation and pyridinyl radical are formed as shown for the case of anthracene in Scheme 15. The latter rapidly decomposes to give pyridine and an ethoxy radical. Evidence for the proposed mechanism was obtained by observation of the absorption spectra of relevant radical cations upon laser flash photolysis of methylene chloride solutions containing sensitizers and pyridinium salt [64]. Moreover, estimates of the free energy change by the Rehm-Weller equation [65] give highly favorable values for anthracene, perylene, phenothiazine and thioxanthone sensitized systems, whilst benzophenone and acetophenone seemed not to be suitable sensitizers (Table 5). The failure of the polymerization experiments sensitized by benzophenone and acetophenone in the absence of a hydrogen donor is consistent with the proposed electron transfer mechanism. 

As phenothiazine and its derivatives are excellent electron donors (see Section III,A, 1), interesting electrical properties are to be expected with these compounds. Phenothiazine itself is a semiconductor as shown by Brown and Aftergut the activation energy is 1.6 ev between 50° and 150° for samples purified by sublimation and zone melting. The electrical parameters are influenced to an important extent by the method of sample preparation. 

As phenothiazine is a good electron donor, there are many papers on the interaction of this compound with various acceptors (see Sections III,A,1, and IV,H,1). In most cases, authentical charge-transfer complexes are obtained however, with very strong acceptors, e.g., 2,3-dichloro-5,6-dicyano-p-benzoquinone, (DDQ), there is total transfer of one electron, leading to It is possible that the same... 

It was mentioned in Section III,A, 1 that, as indicated by the results of quantum mechanical calculations, phenothiazine is an excellent electron donor the numerous examples in the previous subsections dealing with the oxidation of phenothiazines also illustrated the ease with which electrons are lost by the derivatives of this heterocycle. Consequently, phenothiazine charge-transfer complexes with various acceptors are expected. 

In a search for a mechanism of the inhibitory action exerted by chlorpromazine on some enzymatic processes, the interaction of this substance with oxidized flavines and xanthines was investigated, and the formation of charge-transfer complexes was observed. There are many indications that the phenothiazine-melanine interaction, which is probably involved in the retinotoxicity of some phenothiazine drugs, is also of the donor-acceptor type, as suggested... 

In earlier literature there are reports of the formation of perhalides on treatment of phenothiazine with bromine and iodine these are now considered to be charge-transfer complexes. The phenothiazine component normally acts as a donor and the electronegative halogens as acceptors, but here total transfer of electrons occurs and the phenothiazine is oxidized. Phenothiazine and 3,7-dimethylpheno-thiazine behave similarly in the presence of strong organic acceptors, like dicyanobenzoquinone and dichlorodicyanobenzoquinone. ... 

---