Photochemistry excimer formation

The present article reviews the photochemical deactivation modes and properties of electronically excited metallotetrapyrroles. Of the wide variety of complexes possessing a tetrapyrrole ligand and their highly structured systems, the subject of this survey is mainly synthetic complexes of porphyrins, chlorins, corrins, phthalocyanines, and naphthalocyanines. All known types of photochemical reactions of excited metallotetrapyrroles are classified. As criteria for the classification, both the nature of the primary photochemical step and the net overall chemical change, are taken. Each of the classes is exemplified by several recent results, and discussed. The data on exciplex and excimer formation processes involving excited metallotetrapyrroles are included. Various branches of practical utilization of the photochemical and photophysical properties of tetrapyrrole complexes are shown. Motives for further development and perspectives in photochemistry of metallotetrapyrroles are evaluated. 

An important aspect of the photophysics of the Pt(diimine)(dithiolate) photochemistry that has received increasing attention is the ability of the excited-state complexes to undergo self-quenching. Initial work by Connick and Gray (111) showed that the lifetime of the complex Pt(bpy)(bdt) (bdt = benzene-1,2-dithiolate, 31) decreased with increasing solution concentration. The bimolecular self-quenching rate constant, calculated from a Stem-Volmer quenching analysis, was found to be 9.5 x 109 A/-1 s-1 in acetonitrile and 4 x 109 M 1 s 1 in chloroform. However, no evidence of excimer formation... 

The proximity of the chromophores in polymers favours the formation of intramolecular excimers. Since excimer formation takes place at the expense of other photophysical and photochemical processes, it has been suggested that wherever excimer formation is possible the photochemistry of the polymer is likely to be strongly affected. 

Koch and A.H. Jones, A photochemical exchange reaction of Michler s ketone, J. Am. Chem. Soc. 92, 7503 (1970) D.I. Schuster and M.D. Goldstein, Photochemistry of ketones in sol ution. XXXVII. Plash photolysis of Michler s ketone in solution. Rate constants for decay and triplet excimer formation, J. Am. Chem. Soc. 95, 986 (1973) V.D. McGinnis and D.M. Dusek, Photopolymerization of methyl methacrylate with the use of 4,4 BIS (diethylamion) benzophenone as the photoinitiator, ACS Polym. Prepr. 15(1), 480 (1974). 

Pyrene was one of the widely used probes in the initial surface photochemistry studies due to the long hfetime of its monomer, the capacity of excimer formation, and also its spectral sensitivity. The III/I (370 nm/390 nm) vibronic band ratio was successfully used to monitor the microscopic polarity of the adsorbent, either onto silica or alumina [66]. Peak I, the 0-0 band of the 5o 5i absorption, is symmetry forbidden and grows in polar media. In the case of alumina, this surface exhibits a surface polarity similar to the one presented by polar solvents such as methanol [66a]. 

In addition to the rather trivial differences mentioned above, laser irradiation can also lead to products as a result of reexcitaion of the carbenes. Thus, excitation of 30 in isooctane with a pulse of the 249-nm line from a KrF excimer laser results in the formation of 9,10-diphenylanthrancene (103), 9,10-diphenylphenanthrene (104), and fluorene, in addition to tetraphenylethylene (Scheme 9.31). Conventional lamp irradiation of 30 results in the formation of benzophenone azine as a major product. None of the products mentioned above are detected. Moreover, the yield of both 103 and fluorene increased markedly with increased laser power. While the details of the mechanism of this reaction are not certain yet, it is clear from the dependence on laser power that some of these products arise from carbene photochemistry. " ... 

All of the photochemical cycloaddition reactions of the stilbenes are presumed to occur via excited state ir-ir type complexes (excimers, exciplexes, or excited charge-transfer complexes). Both the ground state and excited state complexes of t-1 are more stable than expected on the basis of redox potentials and singlet energy. Exciplex formation helps overcome the entropic problems associated with a bimolecular cycloaddition process and predetermines the adduct stereochemistry. Formation of an excited state complex is a necessary, but not a sufficient condition for cycloaddition. In fact, increased exciplex stability can result in decreased quantum yields for cycloaddition, due to an increased barrier for covalent bond formation (Fig. 2). The cycloaddition reactions of t-1 proceed with complete retention of stilbene and alkene photochemistry, indicative of either a concerted or short-lived singlet biradical mechanism. The observation of acyclic adduct formation in the reactions of It with nonconjugated dienes supports the biradical mechanism. 

Photocycloaddition and photoaddition can be utilized for new carbon-carbon and carbon-heteroatom bond formation under mild conditions from synthetic viewpoints. In last three decades, a large number of these photoreactions between electron-donating and electron-accepting molecules have been appeared and discussed in the literature, reviews, and books [1-10]. In these photoreactions, a variety of reactive intermediates such as excimers, exciplexes, triplexes, radical ion pairs, and free-radical ions have been postulated and some of them have been detected as transient species to understand the reaction mechanism. Most of reactive species in solution have been already characterized by laser flash photolysis techniques, but still the prediction for the photochemical process is hard to visualize. In preparative organic photochemistry, the dilemma that the transient species including emission are hardly observed in the reaction system giving high chemical yields remains in most cases [11,12]. 

Although the phenomenon is more common in organic photochemistry, a coordination entity can also act in the process of excimer or exciplex formation as an excited molecule AB or quencher (Q).The second-sphere donor-acceptor interaction with an acceptor quencher causes oxidative quenching of AB, whereas interaction with a donor quencher yields reductive quenching. 

The importance of bioexcimers (bioexciplexes) in the photochemistry of biological compounds has been also emphasized. Computation of potential energy curves modeling the complex pheophytin-quinone shows the relevance that stabilization caused by the formation of rr-stacked excited dimers, that is, excimers (exciplexes) and the corresponding presence of conical intersections, have to provide... 

Photochemistry, photophysics Solvent-solute interactions, dynamics of micelles, polymer structure and dynamics, characterization of excited states, excimer and exciplex formation Capability to provide information on rapid phenomena... 

We ve seen that bimolecular processes involving excited states can take many forms. Collision can facilitate relaxation to the ground state (quenching) or formation of an excited state complex (exciplex or excimer). Alternatively, bimolecular association can occur prior to excitation, leading to an absorption complex. In this and the next two sections we consider a new outcome for the interactions of an excited state, D, with another molecule, A (Eq. 16.8). Now the result is energy transfer from one molecule to another, producing electronically excited A (A ). Different mechanisms are possible, and these energy transfer processes are very important in photochemistry and other fields. 

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