Charge transfer reactions photochemistry

IV. Redox Reactions and Charge-Transfer State Photochemistry.91... 

Photoinduced charge-transfer reactions have been extensively investigated in many fields of science for more than 15 years. Especially, in the now fast-developing field of photovoltaics it is of fundamental interest to understand the photophysics and photochemistry of excited states in organic molecules [61]. Photosynthetic energy conversion in green plants serves herein as the ultimate prototype [62]. 

The study of molecular systems using quantum mechanics is based on the Born-Oppenheimer approximation. This approximation relies on the fact that the electrons, because of their smaller mass, move much faster than the heavier nuclei, so they follow the motion of the nuclei adiabatically, whereas the latter move on the average potential of the former. The Born-Oppenheimer approximation is sufficient to describe most chemical processes. In fact, our notion of molecular structure is based on the Born-Oppenheimer approximation, because the molecular structure is formed by nuclei being placed in fixed positions. There are, however, essential nonadiabatic processes in nature that cannot be described within this approximation. Nonadiabatic processes are ubiquitous in photophysics and photochemistry, and they govern such important phenomena as photosynthesis, vision, and charge-transfer reactions. 

It has been suggested that P BChl (where BChl is one of the two monomeric or "accessory BChls that are not part of P) is a transient state prior to P "I (14,16,19), although the evidence supporting this view has been criticized (23, 24) Recent subpicosecond studies find no evidence for P "BChl (8,9) These new results do not preclude some involvement of a monomeric BChl in the early photochemistry, only that P BChl apparently is not a kinetically resolved transient state Perhaps P itself contains some charge-transfer character between its component BChls, or between P and one or both of the monomeric BChls (8,9,25-27) One of the two monomeric BChls apparently can be removed by treatment of the reaction center with sodium borohydride (28) and subsequent chromatography, with no impairment of the primary electron transfer reactions (29) Thus, at present it appears that P I is the first resolved radical-pair state, and it forms with a time constant of about 4 ps in Rps sphaeroides ... 

Jeveral aspects of the photolytic behavior of aqueous complex ions have been studied in this laboratory over the past few years. One continually interesting question has been the extent to which the photochemistry of a complex depends on the absorption band irradiated. In the case of Co(III) acidopentamines, such as Co(NH3)5Br+2, we found that irradiation of Ajg —> g) bands showing appreciable charge transfer led to redox and aquation reactions which were competitive. It was reasonable to suppose that the common precursor was the species formed by a prompt heterolytic bond fission (7). The ( Aig —> Tig) band was far less photoactive, and in model cases, irradiation led only to aquation. Each excited state or excited state manifold thus tended to show a distinct photochemistry, which meant that conversion from one excited state to another was not important. 

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. 

The electron transfer photochemistry of benzocyclobutenes in the presence of dienophiles exhibits another interesting feature of CIP reactions [93]. For example, charge transfer irradiation of the EDA complex composed of 1,2-diphenylbenzocy-clobutene (36) and TCNE (IS) leads to the CIP (36 15 ), of which 36 spontaneously ring-opens to the o-xylylene (37) radical cation, followed by the collapse of the new CIP (Eqs. (20, 21)), leading to the Diels-Alder adduct 39 in high yield and with high efficiency. 

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